U.S. patent application number 15/570809 was filed with the patent office on 2018-06-14 for supported metallocene catalyst systems for polymerization.
The applicant listed for this patent is ExxonMobil Chemical Patents Inc.. Invention is credited to Steven D Brown, Xiongdong Lian, Lubin Luo, Jian Yang.
Application Number | 20180162964 15/570809 |
Document ID | / |
Family ID | 56121206 |
Filed Date | 2018-06-14 |
United States Patent
Application |
20180162964 |
Kind Code |
A1 |
Yang; Jian ; et al. |
June 14, 2018 |
Supported Metallocene Catalyst Systems for Polymerization
Abstract
This invention relates to supported metallocene catalyst systems
for polymerization, the catalyst systems comprising asymmetrically
substituted indenyl groups, high surface area supports, and
aluminoxane activators. This invention also relates to methods for
polymerizing olefins, including methods for producing isotactic
polypropylene.
Inventors: |
Yang; Jian; (Houston,
TX) ; Luo; Lubin; (Houston, TX) ; Brown;
Steven D; (League City, TX) ; Lian; Xiongdong;
(Shanghai, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ExxonMobil Chemical Patents Inc. |
Baytown |
TX |
US |
|
|
Family ID: |
56121206 |
Appl. No.: |
15/570809 |
Filed: |
May 27, 2016 |
PCT Filed: |
May 27, 2016 |
PCT NO: |
PCT/US2016/034755 |
371 Date: |
October 31, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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62171630 |
Jun 5, 2015 |
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62206004 |
Aug 17, 2015 |
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62205977 |
Aug 17, 2015 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F 110/06 20130101;
C08F 4/65912 20130101; C08F 10/06 20130101; C07F 17/00 20130101;
C08F 2500/12 20130101; C08F 2500/15 20130101; C08F 110/06 20130101;
C08F 4/65927 20130101; C08F 110/06 20130101; C08F 4/65916 20130101;
C08F 110/06 20130101; C08F 4/6492 20130101; C08F 110/06 20130101;
C08F 2500/01 20130101; C08F 2500/03 20130101; C08F 2500/12
20130101; C08F 110/06 20130101; C08F 2500/03 20130101; C08F 2500/12
20130101; C08F 110/06 20130101; C08F 2500/04 20130101; C08F 2500/12
20130101; C08F 2500/15 20130101; C08F 2500/05 20130101 |
International
Class: |
C08F 10/06 20060101
C08F010/06; C07F 17/00 20060101 C07F017/00 |
Claims
1. An olefin polymerization catalyst system comprising: i) a
metallocene catalyst compound represented by the formula:
##STR00013## wherein R.sup.2 and R.sup.8 are, independently, a
C.sub.1 to C.sub.20 linear alkyl group, provided that at least one
of R.sup.2 and R.sup.8 must have at least 4 carbon atoms; R.sup.4
and R.sup.10 are substituted or unsubstituted aryl groups; M is a
transition metal selected from Group 2, 3, or 4 of the Periodic
Table; T is a bridging group; each X is an anionic leaving group;
each R.sup.1, R.sup.3, R.sup.5, R.sup.6, R.sup.7, R.sup.9,
R.sup.11, R.sup.12, R.sup.13, and R.sup.14 is, independently,
hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl,
substituted halocarbyl, silylcarbyl, substituted silylcarbyl,
germylcarbyl, or substituted germylcarbyl substituents; wherein
either or both of R.sub.5 and R.sub.6 and R.sub.11 and R.sub.12
optionally join together to form a ring structure; and ii) a
support having an average surface area of from about 400 to 800
m.sup.2/g support; and iii) an aluminoxane.
2. The catalyst system of claim 1, wherein the support has: an
average pore diameter of from 60 to 300 Angstrom; at least 20% of
the incremental pore volume comprised of pores having a pore
diameter larger than 100 Angstrom; and an aluminoxane loading of
greater than about 7 mmol Al/g support.
3. The catalyst system of claim 1,wherein the support has: an
average surface area of from about 550 to 650 m.sup.2/g support; an
average pore diameter of from about 80 to 130 Angstrom; an average
pore volume of from about 0.5 to 2.5 ml/g support; and an average
particle size of from about 20 to 200 micrometers.
4. The catalyst system of claim 1, wherein the support comprises
agglomerates of a plurality of primary particles.
5. The catalyst system of claim 1, wherein R.sup.2 is methyl,
ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,
n-nonyl or n-decyl.
6. The catalyst system of claim 1, wherein R.sup.8 is methyl,
ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,
n-nonyl or n-decyl.
7. The catalyst system of claim 1, wherein at least one of R.sup.4
and R.sup.10 is a phenyl group substituted at the 3' and 5'
positions with C.sub.1 to C.sub.10 alkyl groups, aryl groups, or
combinations thereof.
8. The catalyst system of claim 1, wherein R.sup.4 and R.sup.10 are
independently a phenyl group substituted at the 3' and 5' positions
with C.sub.1 to C.sub.10 alkyl groups, aryl groups, or combinations
thereof and, optionally, the 4' position is substituted with a
group selected from (XR'.sub.n).sup.-, wherein X is a heteroatom
selected from Groups 14 to 17 of the Periodic Table and having an
atomic weight of 13 to 79, and R' is one of a hydrogen atom,
halogen atom, a C.sub.1 to C.sub.10 alkyl group or a C.sub.6 to
C.sub.10 aryl group, and n is 0, 1, 2, or 3.
9. The catalyst system of claim 1, wherein at least one of R.sup.4
and R.sup.10 is a phenyl group substituted at the 2' position with
an alkyl or aryl group.
10. The catalyst system of claim 1, wherein one of R.sub.5 and
R.sub.6 or R.sub.11 and R.sub.12 join together to form a ring
structure.
11. The catalyst system of claim 1, wherein each X is,
independently, selected from the group consisting of hydrocarbyl
radicals having from 1 to 20 carbon atoms, hydrides, amides,
alkoxides, sulfides, phosphides, halides, dienes, amines,
phosphines, ethers, and a combination thereof and two X may form a
part of a fused ring or a ring system.
12. The catalyst system of claim 1, wherein T is represented by the
formula R.sup.a.sub.2J, where J is C, Si, or Ge, each R.sup.a is,
independently, hydrogen, halogen, C.sub.1 to C.sub.20 hydrocarbyl
or a C.sub.1 to C.sub.20 substituted hydrocarbyl, and two R.sup.a
optionally form a cyclic structure including aromatic, partially
saturated, or saturated cyclic or fused ring system.
13. The catalyst system of claim 1, wherein T is CH.sub.2,
CH.sub.2CH.sub.2, C(CH.sub.3).sub.2, SiMe.sub.2, SiPh.sub.2,
SiMePh, Si(CH.sub.2).sub.3, Si(CH.sub.2).sub.4,
Si(Me.sub.3SiPh).sub.2, or Si(CH.sub.2).sub.5.
14. The catalyst system of claim 1, wherein the metallocene
catalyst compound is represented by one or more of the following
compounds: ##STR00014## ##STR00015##
15. The catalyst system of claim 1, wherein the alumoxane is
present at a molar ratio of aluminum to metallocene catalyst
compound transition metal of 100:1 or more.
16. The catalyst system of claim 1, wherein the rac/meso ratio is
10:1 or greater.
17. The catalyst system of claim 1, further comprising an aluminum
alkyl.
18. A process to polymerize olefins comprising contacting one or
more olefins with the catalyst system of claim 1 in a reactor and
recovering a polymer.
19. The process of claim 18, wherein hydrogen is not added to the
reactor.
20. A process to produce isotactic polypropylene, the process
comprising contacting the catalyst system of claim 1, with
propylene and obtaining isotactic polypropylene.
21. The process of claim 20, further comprising contacting the
catalyst system with propylene at a first hydrogen concentration in
the reactor, adjusting to a second hydrogen concentration, and
recovering isotactic polypropylene having a bimodal molecular
weight distribution.
22. The process of claim 21, further comprising contacting the
isotactic polypropylene with ethylene and optional comonomer to
produce an impact copolymer.
23. The process of claim 21, wherein the isotactic polypropylene
has a melt flow rate (MFR, ASTM D-1238, 2.16 kg and 230.degree. C.)
of less than about 0.3 dg/min.
24. The process of claim 20, wherein the catalyst activity is at
least 3000 g polymer/g catalysthr and the molecular weight, Mw, of
the isotactic polypropylene is at least 600 kg/mol.
25. The process of claim 20, wherein the catalyst activity is at
least 4000 g polymer/g catalysthr and the molecular weight, Mw, of
the isotactic polypropylene is at least 1400 kg/mol.
26. The process of claim 20, wherein the isotactic polypropylene
has a melting temperature, Tm, DSC peak second melt, of at least
151.degree. C.
27. The catalyst system of claim 1, wherein: a) the support has: i)
an average pore diameter of from 60 to 300 Angstrom; ii) at least
20% of the incremental pore volume comprised of pores having a pore
diameter larger than 100 Angstrom; and iii) an aluminoxane loading
of greater than about 7 mmol Al/g support; b) the support comprises
agglomerates of a plurality of primary particles; c) R.sup.2 is
methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl,
n-octyl, n-nonyl or n-decyl; d) R.sup.8 is methyl, ethyl, n-propyl,
n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl;
and e) at least one of R.sup.4 and R.sup.10 is a phenyl group
substituted at the 3' and 5' positions with C.sub.1 to C.sub.10
alkyl groups, aryl groups, or combinations thereof.
28. The catalyst system of claim 1, wherein: a) the support has: i)
an average surface area of from about 550 to 650 m.sup.2/g support;
ii) an average pore diameter of from about 80 to 130 Angstrom; iii)
an average pore volume of from about 0.5 to 2.5 ml/g support; iv)
an average particle size of from about 20 to 200 micrometers; b)
the support comprises agglomerates of a plurality of primary
particles; c) R.sup.2 is methyl, ethyl, n-propyl, n-butyl,
n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl; d)
R.sup.8 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,
n-heptyl, n-octyl, n-nonyl or n-decyl; and e) R.sup.4 and R.sup.10
are independently a phenyl group substituted at the 3' and 5'
positions with C.sub.1 to C.sub.10 alkyl groups, aryl groups, or
combinations thereof and, optionally, the 4' position is
substituted with a group selected from (XR'.sub.n).sup.-, wherein X
is a heteroatom selected from Groups 14 to 17 of the Periodic Table
and having an atomic weight of 13 to 79, and R' is one of a
hydrogen atom, halogen atom, a C.sub.1 to C.sub.10 alkyl group or a
C.sub.6 to C.sub.10 aryl group, and n is 0, 1, 2, or 3.
29. The catalyst system of claim 27, wherein each X is,
independently, selected from the group consisting of hydrocarbyl
radicals having from 1 to 20 carbon atoms, hydrides, amides,
alkoxides, sulfides, phosphides, halides, dienes, amines,
phosphines, ethers, and a combination thereof and two X may form a
part of a fused ring or a ring system; and T is represented by the
formula R.sup.a.sub.2J, where J is C, Si, or Ge, each R.sup.a is,
independently, hydrogen, halogen, C.sub.1 to C.sub.20 hydrocarbyl
or a C.sub.1 to C.sub.20 substituted hydrocarbyl, and two R.sup.a
optionally form a cyclic structure including aromatic, partially
saturated, or saturated cyclic or fused ring system.
30. A process to polymerize olefins comprising contacting one or
more olefins with the catalyst system of claim 27 in a reactor and
recovering a polymer.
31. A process to produce isotactic polypropylene, the process
comprising contacting the catalyst system of claim 28 with
propylene and obtaining isotactic polypropylene.
32. A process to produce isotactic polypropylene, the process
comprising contacting the catalyst system of claim 29 with
propylene and obtaining isotactic polypropylene.
Description
PRIORITY
[0001] This application claims priority to and the benefit of U.S.
Ser. No. 62/205,977, filed Aug. 17, 2015; U.S. Ser. No. 62/206,004,
filed Aug. 17, 2015; and U.S. Ser. No. 62/171,630, filed Jun. 5,
2015.
CROSS REFERENCE TO RELATED APPLICATIONS
[0002] This invention also relates to: concurrently filed PCT
Application ______ (Atty. Docket 2016EM112), entitled "Metallocene
Catalyst Compositions and Polymerization Process Therewith;" PCT
Application ______ (Atty. Docket 2016EM113), entitled "Single
Reactor Production of Polymers in Gas or Slurry Phase;" and PCT
Application ______ (Atty. Docket 2016EM114), entitled "Production
of Heterophasic Polymers in Gas or Slurry Phase."
FIELD OF THE INVENTION
[0003] This invention relates to supported metallocene catalyst
systems for polymerization, the catalyst systems comprising
asymmetrically substituted indenyl groups, high surface area
supports, and aluminoxane activators. This invention also relates
to methods for polymerizing olefins, including methods for
producing isotactic polypropylene.
BACKGROUND OF THE INVENTION
[0004] Recently, efforts have been made to prepare heterophasic
copolymers, such as an impact copolymer (ICP), using newly
developed metallocene (MCN) catalysis technology to capitalize on
the benefits such catalysts provide. Homopolymers prepared with
such "single-site" catalysts often have a narrow molecular weight
distribution (MWD), low extractables, and a variety of other
favorable properties associated therewith, and copolymers often
also have narrow composition distributions.
[0005] Unfortunately, MCN catalysts for polypropylene have
generally been limited by their inability to produce isotactic
polypropylene (iPP) or propylene-ethylene copolymers of high
molecular weight or other desired properties. Compared to their
Ziegler-Natta (ZN) catalyzed counterparts, the iPP matrix of the
ICP prepared using MCN has a low porosity, and is unable to hold a
sufficiently high rubber content within the iPP matrix required for
toughness and impact resistance. The formation of rubber in a
separate phase outside the matrix is undesirable, e.g., it can
result in severe reactor fouling.
[0006] A key enabling factor to making an improved ICP with step
out properties is to obtain an MCN catalyst system capable of
making an iPP matrix with stiffness properties comparable to or
better than conventional ZN-catalyzed iPP. To provide efficiency
and flexibility for commercial polymerization processes, this
catalyst system should also be capable of producing high molecular
weight polymer at high catalyst activities in the presence of low
or zero hydogen concentrations. Such a catalyst system optimizes
flexibility for production of different polymer grades, because
hydrogen concentration can be used as a lever to reduce molecular
weight in the reactor. Unfortunately, MCN catalyst systems often
have low activities at low or zero hydrogen concentrations. While
addition of hydrogen increases MCN catalyst activities, it can also
result in polymers with lower molecular weights than what is
desirable.
[0007] A further disadvantage of MCN catalysts is the requirement
of large amounts of expensive activator, such as an aluminoxane, to
activate the catalysts. Additionally, while homogeneous metallocene
catalysts can be used in solution phase reactors, MCN catalysts
generally need to be supported to be used in most other
polymerization processes. Thus, while many metallocene catalysts
are capable of making polyolefins with commercially desirable
properties, the catalysts are often not practical or economical on
an industrial scale due to the large amount of activator needed and
difficulties in incorporating the catalyst and activator on a
support.
[0008] It is important to find a way to incorporate the MCN and
cocatalyst onto the support without losing the advantages of the
homogenous MCN compound, including high catalyst activity,
stereochemical control, and the ability to tailor polymer
properties. Identifying the optimum properties for MCN catalyst
supports is an area of significant research interest. Both the
nature of the support and the method used to integrate the support
and/or activator can affect the catalyst activity and the final
properties of the polymer.
[0009] Although aluminoxanes are expensive, supported catalysts
with higher aluminoxane loadings are desirable in some
circumstances. For example, when the metallocene compound has low
activity or low activation efficiency or when a multi-catalyst
precursor system is used where the total catalyst precursor
loadings are higher than usual, higher aluminoxane loading may be
required to achieve a commercially viable catalyst activity. In
polymerization processes where liquid solvent is present, such as
slurry and condensed mode processes, methyl aluminoxane (MAO) is
soluble in the solvent and can leach out of the silica particles.
It has generally not been possible with conventional silicas, e.g.,
Grace 948 or 955, PQ ES 70 or ES 757, to load more than about 8 to
9 mmol Al/g of silica onto the support without leaching of MAO (and
possibly catalyst) into the solvent medium. This leaching can cause
fouling and fines in the reactor system and can negatively impact
catalyst activity and polymer properties.
[0010] It is also important for a catalyst support to be able to
retain mechanical strength under the operating conditions of the
process in which it is used. Many polymerization processes take
place at significantly higher than ambient temperatures and
pressures. If the mechanical strength of the support is
compromised, the impregnated silica particles can fragment. This
can also lead to activator and catalyst leaching into the solvent
medium. Additionally, polymerization can start to take place on the
smaller fragmented particles, leading to agglomerates within the
reactor system that can cause fouling, plugging, and other
problems.
[0011] There is a need for supported MCN catalyst systems capable
of polymerizing polymers with high molecular weights at low or zero
hydrogen concentrations and high catalyst activities. There is a
need for supports compatible with such catalyst systems that can
maintain the mechanical strength necessary for a variety of
polymerization process and load sufficient activator, e.g.,
aluminoxane, to achieve high catalyst activities.
SUMMARY OF THE INVENTION
[0012] This invention relates to supported metallocene catalyst
systems and uses thereof, the catalyst systems comprising
asymmetrically substituted indenyl groups, high surface area
supports, and aluminoxane activators.
[0013] Specifically, this invention is directed to olefin
polymerization catalyst systems comprising: [0014] i) a MCN
catalyst compound represented by the formula:
[0014] ##STR00001## [0015] wherein R.sup.2 and R.sup.8 are,
independently, a C.sub.1 to C.sub.20 linear alkyl group, provided
that at least one of R.sup.2 and R.sup.8 must have at least 4
carbon atoms; [0016] R.sup.4 and R.sup.10 are substituted or
unsubstituted aryl groups; [0017] M is a transition metal selected
from Group 2, 3, or 4 of the Periodic Table; [0018] T is a bridging
group; [0019] each X is an anionic leaving group; [0020] each
R.sup.1, R.sup.3, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.11,
R.sup.12, R.sup.13, and R.sup.14 is, independently, hydrogen, or a
hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted
halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or
substituted germylcarbyl substituents; [0021] wherein either or
both of R.sub.5 and R.sub.6 and R.sub.11 and R.sub.12 optionally
join together to form a ring structure; and [0022] ii) a support
having an average surface area of from about 400 to 800 m.sup.2/g;
and [0023] iii) an aluminoxane.
[0024] This invention is also directed to processes for
polymerizing olefins, using the catalyst systems disclosed herein,
including processes for producing iPP. The processes generally
comprise contacting one or more olefins, such as propylene, with a
catalyst system comprising an activator and a MCN catalyst compound
according to the formula above, and obtaining a polymer. This
invention is also directed to processes for producing impact
copolymers comprising further contacting iPP with ethylene and
optional comonomer to produce the impact copolymer. The processes
may involve staged hydrogen addition, comprising contacting the
catalyst system with propylene at a first hydrogen concentration in
the reactor, and then adjusting to a second hydrogen concentration
and obtaining iPP having a bimodal molecular weight
distribution.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] FIG. 1 is an electron micrograph showing D 150-60A silica
comprising agglomerated primary particles.
[0026] FIG. 2 is an electron micrograph showing PD 13054 silica
comprising agglomerated primary particles.
[0027] FIG. 3 is an electron micrograph showing a comparative MS
3050 silica.
[0028] FIG. 4 is a graph of molecular weight distribution for a
bimodal iPP (Run 8 in Table 6) made using a catalyst system
according to the invention.
DEFINITIONS
[0029] For purposes of this disclosure and the claims appended
thereto, the new numbering scheme for the Periodic Table Groups is
used as described in CHEMICAL AND ENGINEERING NEWS, 63(5), p. 27,
(1985).
[0030] For purposes herein, particle size (PS), and distributions
thereof, are determined by laser diffraction using a MASTERSIZER
3000 (range of 1 to 3500 .mu.m) available from Malvern Instruments,
Ltd., Worcestershire, England, or an LS 13 320 MW with a micro
liquid module (range of 0.4 to 2000 .mu.m) available from Beckman
Coulter, Inc., Brea, California. Average PS refers to the
distribution of particle volume with respect to particle size.
Unless otherwise indicated expressly or by context, "particle"
refers to the overall particle body or assembly such as an
aggregate, agglomerate, or encapsulated agglomerate, rather than
subunits or parts of the body, such as the primary particles in
agglomerates or the elementary particles in an aggregate.
[0031] For purposes herein, the surface area (SA, also called the
specific surface area or BET surface area), pore volume (PV), and
pore diameter (PD) of catalyst support materials are determined by
the Brunauer-Emmett-Teller (BET) method using adsorption-desorption
of nitrogen (temperature of liquid nitrogen: 77 K) with a
MICROMERITICS TRISTAR II 3020 instrument or MICROMERITICS ASAP 2420
instrument after degassing of the powders for 4 to 8 hours at 100
to 300.degree. C. for raw/calcined silica or 4 hours to overnight
at 40 to 100.degree. C. for silica supported aluminoxane. More
information regarding the method can be found, for example, in
"Characterization of Porous Solids and Powders: Surface Area, Pore
Size and Density," S. Lowell et al., Springer, 2004. PV refers to
the total PV, including both internal and external PV.
[0032] The term "agglomerate" as used herein refers to a material
comprising an assembly of primary particles held together by
adhesion, i.e., characterized by weak physical interactions such
that the particles can easily be separated by mechanical forces,
e.g., particles joined together mainly at corners or edges. The
term "primary particles" refers to the smallest, individual
disagglomerable units of particles in an agglomerate (without
fracturing), and may in turn be an encapsulated agglomerate, an
aggregate or a monolithic particle. Agglomerates are typically
characterized by having an SA not appreciably different from that
of the primary particles of which it is composed. Silica
agglomerates are prepared commercially, for example, by a spray
drying process.
[0033] FIGS. 1 and 2 show examples of encapsulated agglomerates 10,
which, as seen in the partially opened particles, are comprised of
a plurality of primary particles 12. FIG. 1 shows an electron
micrograph of D 150-60A silica (Asahi Glass Co., Ltd. Or AGC
Chemicals Americas, Inc.), which appears as generally spherical
particles or grains 10, which, as seen in a partially opened
particle, are actually agglomerates comprised of a plurality of
substructures or primary particles 12 within the outer spherical
shell or aggregate surface 14 that partially or wholly encapsulates
the agglomerates. Likewise, FIG. 2 is an electron micrograph of PD
13054 (PQ Corporation) showing interior agglomerates 10 comprised
of around 5-50 .mu.m primary particles 12 and encapsulating
aggregate 14. The examples shown are for illustrative purposes only
and the sizes of the particles shown may not be representative of a
statistically larger sample; the majority of the primary particles
in this or other commercially available silicas may be larger or
smaller than the image illustrated, e.g., 2 .mu.m or smaller,
depending on the particular silica production process employed by
the manufacturer.
[0034] "Aggregates" are an assembly of elementary particles sharing
a common crystalline structure, e.g., by a sintering or other
physico-chemical process such as when the particles grow together.
Aggregates are generally mechanically unbreakable, and the specific
surface area of the aggregate is substantially less than that of
the corresponding elementary particles. An "elementary particle"
refers to the individual particles or grains in or from which an
aggregate has been assembled. For example, the primary particles in
an agglomerate may be elementary particles or aggregates of
elementary particles. For more information on agglomerates and
aggregates, see Walter, D., Primary
Particles--Agglomerates--Aggregates, in Nanomaterials (ed Deutsche
Forschungsgemeinschaft), Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim, Germany, doi: 10.1002/9783527673919, pp. 1-24 (2013).
[0035] The terms "monolith" or "monolithic" refer to a material
formed of a single mass of material, and include aggregates as well
as bulk materials without any defined geometry or grain structure.
FIG. 3 shows a comparative support MS 3050, comprised of generally
spherical particles 20 with an entirely aggregated or monolithic
core 22, lacking the agglomerated primary particles and internal
pore morphology of the FIG. 1-2 supports.
[0036] The terms "capsule" or "encapsulated" or "microencapsulated"
are used interchangeably herein to refer to an agglomerate in the
1-1000 .mu.m size range comprising an exterior surface that is
coated or otherwise has a physical barrier that inhibits
disagglomeration of the primary particles from the interior of
microencapsulated agglomerate. The barrier or coating may be an
aggregate, for example, of primary and/or elementary particles
otherwise constituted of the same material as the agglomerate.
FIGS. 1-2 show examples of microencapsulated agglomerates 10
comprised of a plurality of primary particles 12 within an outer
aggregate surface or shell 14 that partially or wholly encapsulates
the agglomerates, in which the primary particles may be allowed to
disagglomerate by fracturing, breaking, dissolving, chemically
degrading or otherwise removing all or a portion of the shell
14.
[0037] In the case of spray dried, amorphous, hydrated-surface
silica as one example, the agglomerates 10 may typically have an
overall size range of 1-300 .mu.m (e.g., 30-200 .mu.m), the primary
particles 12 a size range of 0.001-50 .mu.m (e.g., 50-400 nm or
1-50 .mu.m), and the elementary particles a size range of 1-400 nm
(e.g., 5-40 nm). As used herein, "spray dried" refers to metal
oxide such as silica obtained by expanding a sol in such a manner
as to evaporate the liquid from the sol, e.g., by passing the
silica sol through a jet or nozzle with a hot gas.
[0038] As used herein, Mn is number average molecular weight, Mw is
weight average molecular weight, Mz is z average molecular weight,
wt % is weight percent, and mol % is mole percent. Molecular weight
distribution (MWD), also referred to as polydispersity (PDI), is
defined to be Mw divided by Mn. Unless otherwise noted, all
molecular weights (e.g., Mw, Mn, and Mz) are g/mol and are
determined as described below.
[0039] A metallocene catalyst is defined as an organometallic
compound with at least one .pi.-bound cyclopentadienyl moiety (or
substituted cyclopentadienyl moiety) and more frequently two
.pi.-bound cyclopentadienyl moieties or substituted
cyclopentadienyl moieties.
[0040] "Asymmetric" as used in connection with the instant indenyl
compounds means that the substitutions at the 4 positions are
different, or the substitutions at the 2 positions are different,
or the substitutions at the 4 positions are different and the
substitutions at the 2 positions are different.
[0041] Amounts of rac and meso isomers in the MCN catalyst compound
are determined by proton NMR. Specifically, .sup.1H NMR data are
collected at 23.degree. C. in a 5 mm probe using a 400 MHz Bruker
spectrometer with deuterated methylene chloride or deuterated
benzene. Data is recorded using a maximum pulse width of
45.degree., 8 seconds between pulses and signal averaging 16
transients. The spectrum is normalized to protonated methylene
chloride in the deuterated methylene chloride, which is expected to
show a peak at 5.32 ppm.
[0042] The terms "hydrocarbyl radical", "hydrocarbyl" and
"hydrocarbyl group" are used interchangeably throughout this
document. Likewise, the terms "group", "radical", and "substituent"
are also used interchangeably in this document. For purposes of
this disclosure, "hydrocarbyl radical" is defined to be a radical,
which contains hydrogen atoms and up to 100 carbon atoms and which
may be linear, branched, or cyclic, and when cyclic, aromatic or
non-aromatic.
[0043] A substituted hydrocarbyl radical is a hydrocarbyl radical
where at least one hydrogen has been replaced by a heteroatom or
heteroatom containing group.
[0044] Halocarbyl radicals are radicals in which one or more
hydrocarbyl hydrogen atoms have been substituted with at least one
halogen (e.g., F, Cl, Br, I) or halogen-containing group (e.g.,
CF.sub.3).
[0045] Silylcarbyl radicals (also called silylcarbyls) are groups
in which the silyl functionality is bonded directly to the
indicated atom or atoms. Examples include SiH.sub.3, SiH.sub.2R*,
SiHR*.sub.2, SiR*.sub.3, SiH.sub.2(OR*), SiH(OR*).sub.2,
Si(OR*).sub.3, SiH.sub.2(NR*.sub.2), SiH(NR*.sub.2).sub.2,
Si(NR*.sub.2).sub.3, and the like, where R* is independently a
hydrocarbyl or halocarbyl radical and two or more R* may join
together to form a substituted or unsubstituted saturated,
partially unsaturated or aromatic cyclic or polycyclic ring
structure.
[0046] Germylcarbyl radicals (also called germylcarbyls) are groups
in which the germyl functionality is bonded directly to the
indicated atom or atoms. Examples include GeH.sub.3, GeH.sub.2R*,
GeHR*.sub.2, GeR*.sub.3, GeH.sub.2(OR*), GeH(OR*).sub.2,
Ge(OR*).sub.3, GeH.sub.2(NR*.sub.2), GeH(NR*.sub.2).sub.2,
Ge(NR*.sub.2).sub.3, and the like, where R* is independently a
hydrocarbyl or halocarbyl radical and two or more R* may join
together to form a substituted or unsubstituted saturated,
partially unsaturated or aromatic cyclic or polycyclic ring
structure.
[0047] An aryl group is defined to be a single or multiple fused
ring group where at least one ring is aromatic. Examples of aryl
and substituted aryl groups include phenyl, naphthyl, anthracenyl,
methylphenyl, isopropylphenyl, tert-butylphenyl, cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, carbazolyl, indolyl, pyrrolyl,
and cyclopenta[b]thiopheneyl. Preferred aryl groups include phenyl,
benzyl, carbazolyl, naphthyl, and the like.
[0048] In using the terms "substituted cyclopentadienyl", or
"substituted indenyl", or "substituted aryl", the substitution to
the aforementioned is on a bondable ring position, and each
occurrence is selected from hydrocarbyl, substituted hydrocarbyl,
halocarbyl, substituted halocarbyl, silylcarbyl, germylcarbyl, a
halogen radical, or a polar group. A "bondable ring position" is a
ring position that is capable of bearing a substituent or bridging
substituent. For example, cyclopenta[b]thienyl has five bondable
ring positions (at the carbon atoms) and one non-bondable ring
position (the sulfur atom); cyclopenta[b]pyrrolyl has six bondable
ring positions (at the carbon atoms and at the nitrogen atom).
Thus, in relation to aryl groups, the term "substituted" indicates
that a hydrogen group has been replaced with a hydrocarbyl,
substituted hydrocarbyl, halocarbyl, substituted halocarbyl,
silylcarbyl, germylcarbyl, a halogen radical, or a polar group. For
example, "methyl phenyl" is a phenyl group having had a hydrogen
replaced by a methyl group.
[0049] For purposes of this disclosure, room temperature (RT) is
23.degree. C.
DETAILED DESCRIPTION
[0050] This invention relates to supported MCN olefin
polymerization catalyst systems comprising asymmetrically
substituted indenyl groups, high surface area supports, and
aluminoxane activators, and uses thereof. Specifically, this
invention is directed to olefin polymerization catalyst systems
comprising: [0051] i) a MCN catalyst compound represented by the
formula:
[0051] ##STR00002## [0052] wherein R.sup.2 and R.sup.8 are,
independently, a C.sub.1 to C.sub.20 linear alkyl group, provided
that at least one of R.sup.2 and R.sup.8 has at least 4 carbon
atoms, preferably at least 6 carbon atoms, and preferably R.sup.2
and R.sup.8 have no branches at the alpha or beta positions; [0053]
R.sup.4 and R.sup.10 are substituted or unsubstituted aryl groups
(such as substituted or unsubstituted phenyl groups, preferably
substituted phenyl groups), preferably at least one of the aryl
groups is: 1) substituted at an othro position with at least one
group selected from C.sub.1 to C.sub.40 hydrocarbyls, heteroatoms,
and heteroatom containing groups and/or 2) substituted at the 3',
4' or 5' position with at least one group selected from C.sub.1 to
C.sub.40 hydrocarbyls, heteroatoms, and heteroatom containing
groups; [0054] M is a transition metal selected from Group 2, 3, or
4 of the Periodic Table, preferably a Group 4 transition metal;
[0055] T is a bridging group; [0056] each X is an anionic leaving
group; [0057] each R.sup.1, R.sup.3, R.sup.5, R.sup.6, R.sup.7,
R.sup.9, R.sup.11, R.sup.12, R.sup.13, and R.sup.14 is,
independently, hydrogen, or a hydrocarbyl, substituted hydrocarbyl,
halocarbyl, substituted halocarbyl, silylcarbyl, substituted
silylcarbyl, germylcarbyl, or substituted germylcarbyl
substituents; [0058] wherein either or both of R.sub.5 and R.sub.6
and R.sub.11 and R.sub.12 optionally join together to form a ring
structure; and [0059] ii) a support having an average surface area
of from about 400 to 800 m.sup.2/g; and [0060] iii) an
aluminoxane.
[0061] The MCN catalyst systems disclosed herein produce high
molecular weight polymers at high catalyst activities in the
presence of low or zero hydrogen concentrations. For example, the
catalyst systems can produce high molecular weight iPP, including
bimodal iPP, with excellent stiffness properties and a melt flow
rate (MFR) in the range of interest for ICP applications. The high
surface area supports of the MCN catalyst systems disclosed herein
enable higher activator loading on the supports than what has
conventionally been possible, which is believed to contribute to
the high catalyst activities achieved.
[0062] This invention is also directed to processes for
polymerizing olefins, including processes for producing iPP. The
processes generally comprise contacting one or more olefins, such
as propylene, with a catalyst system comprising an activator and a
MCN catalyst compound according to the formula above, and obtaining
a polymer. This contacting may be done in a reactor in the absence
of any hydrogen added to the reactor. This invention is also
directed to processes for producing impact copolymers comprising
further contacting iPP with ethylene to produce the impact
copolymer. The processes may involve staged hydrogen addition,
comprising contacting the catalyst system with propylene at a first
hydrogen concentration in the reactor, and then adjusting to a
second hydrogen concentration and obtaining iPP having a bimodal
molecular weight distribution.
[0063] The catalyst systems of the invention are particularly
useful for making bimodal iPP in slurry phase processes. A known
process for making bimodal iPP in slurry phase involves two slurry
loop reactors and typically utilizes a ZN catalyst system. The high
molecular weight (HMW) component of the bimodal iPP is made in a
first slurry loop reactor and the low molecular weight (LMW)
component is made in a second slurry loop reactor. In such
processes, the first slurry loop reactor requires no or very low
hydrogen concentrations because a HMW polymer is desired and
hydrogen lowers the molecular weight of the polymer formed.
Hydrogen may be used more liberally in the second slurry loop
reactor where an LMC polymer is desired. Thus, the capability of
the catalyst systems of the invention to produce high molecular
weight polymers at high catalyst activities and no or low hydrogen
concentrations is particularly useful in these processes.
[0064] Preferred embodiments of the catalyst system and associated
components are described in more detail below.
[0065] Metallocene Catalyst Compounds: This invention is directed
to olefin polymerization catalyst systems comprising an MCN
catalyst compound represented by the formula:
##STR00003## [0066] wherein R.sup.2 and R.sup.8 are, independently,
a C.sub.1 to C.sub.20 linear alkyl group, provided that at least
one of R.sup.2 and R.sup.8 has at least 4 carbon atoms, preferably
at least 6 carbon atoms, and preferably R.sup.2 and R.sup.8 have no
branches at the alpha or beta positions; [0067] R.sup.4 and
R.sup.10 are substituted or unsubstituted aryl groups, such as
substituted or unsubstituted phenyl groups, and preferably
substituted phenyl groups (such as substituted or unsubstituted
phenyl groups, preferably substituted phenyl groups), preferably at
least one of the aryl groups is: 1) substituted at an othro
position with at least one group selected from C.sub.1 to C.sub.40
hydrocarbyls, heteroatoms, and heteroatom containing groups and/or
2) substituted at the 3', 4' or 5' position with at least one group
selected from C.sub.1 to C.sub.40 hydrocarbyls, heteroatoms, and
heteroatom containing groups; [0068] M is a transition metal
selected from Group 2, 3, or 4 of the Periodic Table, and
preferably a Group 4 transition metal; [0069] T is a bridging
group; [0070] each X is an anionic leaving group; [0071] each
R.sup.1, R.sup.3, R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.11,
R.sup.12, R.sup.13, and R.sup.14 is, independently, hydrogen, or a
hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted
halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or
substituted germylcarbyl substituents; and [0072] either or both of
R.sub.5 and R.sub.6 and R.sub.11 and R.sub.12 optionally join
together to form a ring structure.
[0073] M may be Hf, Ti and/or Zr, particularly Hf and/or Zr,
particularly Zr.
[0074] R.sup.2 may be a linear C.sub.1-C.sub.10 alkyl group, such
as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl,
n-octyl, n-nonyl or n-decyl) which may be halogenated, preferably
with I, F, Cl or Br.
[0075] R.sup.8 may be a linear C.sub.1-C.sub.10 alkyl group,
preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,
n-heptyl, n-octyl, n-nonyl or n-decyl) which may be halogenated,
preferably with I, F, Cl or Br.
[0076] R.sup.2 and R.sup.8 may be the same linear alkyl group, such
as n-butyl, n-hexyl, and so forth. Additionally, R.sup.2 and
R.sup.8 may be different. For example, R.sup.2 may be methyl and
R.sup.8 may be n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and
so forth.
[0077] The term "substituted phenyl group" means a phenyl that is
substituted with 1, 2, 3, 4, or 5 C.sub.1 to C.sub.20 substituted
or unsubstituted hydrocarbyl groups, such as methyl, ethyl, propyl,
butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,
dodecyl, phenyl, substituted phenyl, biphenyl, or an isomer
thereof. In useful embodiments, the phenyl group is substituted at
the meta or para positions, preferably the 3' and/or 5' positions,
and preferably with C.sub.4 to C.sub.12 alkyl groups. The phenyl
group may also be substituted at the 2' position, but is preferably
not substituted at both the 2' and 6' positions. In other words, in
a preferred embodiment of the invention, when the 2' position of
the phenyl is substituted, the 6' position is hydrogen. The phenyl
group may be substituted at the 4' position with a group of the
formula (XR'.sub.n).sup.-, wherein X is a Group 14, 15 16, or 17
heteroatom; R' is a hydrogen atom, halogen atom, a C.sub.1-C.sub.10
alkyl group, or a C.sub.6-C.sub.10 aryl group; n is 0, 1, 2, or 3;
--NR'.sub.2, --SR', --OR', --OSiR'.sub.3, --SiR'.sub.3, or
--PR'.sub.2; and optionally one or more of the remaining positions
on the phenyl are substituted, such as the 2', 3' and or 5'
positions.
[0078] In another aspect the 4' position on the aryl group is not a
C.sub.4 group, alternately is not a hydrocarbyl group.
[0079] R.sup.4 and R.sup.10 may be independently substituted phenyl
groups, preferably phenyl groups substituted with C.sub.1 to a
C.sub.10 alkyl groups (such as t-butyl, sec-butyl, n-butyl,
isopropyl, n-propyl, cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cycloheptyl, cyclooctyl, phenyl, mesityl, or
adamantyl), or an aryl group which may be further substituted with
an aryl group, and the two aryl groups bound together can be joined
together directly or by linker groups, wherein the linker group is
an alkyl, vinyl, phenyl, alkynyl, silyl, germyl, amine, ammonium,
phosphine, phosphonium, ether, thioether, borane, borate, alane, or
aluminate groups.
[0080] At least one of R.sup.4 and R.sup.10 may be a phenyl group
substituted at the 3' and 5' positions with C.sub.1 to C.sub.10
alkyl groups, aryl groups, or combinations thereof.
[0081] At least one of R.sup.4 and R.sup.10 may be a phenyl group
substituted at the 2' position with an alkyl or an aryl group, such
as another phenyl group.
[0082] At least one of R.sup.4 and R.sup.10 may be a phenyl group
substituted at the 3' and 5' positions and at least one of R.sup.4
and R.sup.10 may be a phenyl group substituted at the 2' position
with an alkyl or aryl group, such as another phenyl group.
[0083] At least one of R.sup.4 and R.sup.10 may be a phenyl group
substituted at the 3' and 5' positions with C.sub.1 to a C.sub.10
alkyl groups, such as a tertiary butyl group.
[0084] At least one of R.sup.4 and R.sup.10 may be a phenyl group
substituted at the 3' and 5' positions with a C.sub.1 to C.sub.10
alkyl group, such as a tertiary butyl group, and at least one of
R.sup.4 and R.sup.10 may be a phenyl group substituted at the 2'
position with an alkyl or an aryl group, such as a phenyl
group.
[0085] At least one of R.sup.4 and R.sup.10 may be a phenyl group
substituted at the 3' and 5' positions with C.sub.1 to C.sub.10
alkyl groups, such as a tertiary butyl group, and optionally at the
4' position with (XR'.sub.n).sup.-, wherein X is a Group 14, 15,
16, or 17 heteroatom having an atomic weight of 13 to 79; R' may be
one of a hydrogen atom, halogen atom, a C.sub.1-C.sub.10 alkyl
group, or a C.sub.6-C.sub.10 aryl group; and n may be 0, 1, 2, or
3, such as methoxy; and at least one of R.sup.4 and R.sup.10 may be
a phenyl group substituted at the 2' position with an alkyl or an
aryl group, such as another phenyl group.
[0086] Both R.sup.4 and R.sup.10 may be a phenyl group substituted
at the 3' and 5' positions with C.sub.1 to C.sub.10 alkyl groups,
such as a tertiary butyl group.
[0087] At least one of R.sup.4 and R.sup.10 may be a phenyl group
substituted at the 3' and 5' positions with aryl groups, such as
substituted or unsubstituted phenyl groups.
[0088] Both R.sup.4 and R.sup.10 may be a phenyl group substituted
at the 3' and 5' positions with aryl groups, such as substituted or
unsubstituted phenyl groups.
[0089] At least one of R.sup.4 and R.sup.10 may be an aryl group
substituted at 3' and 5' positions with C.sub.1 to C.sub.10 alkyl
groups (such as t-butyl, sec-butyl, n-butyl, isopropyl, n-propyl,
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,
cyclooctyl, phenyl, mesityl, or adamantyl) or aryl groups and
combinations thereof, wherein when R.sup.4 or R.sup.10 is a phenyl
group that is further substituted with an aryl group, the two
groups bound together can be joined directly or by linker groups,
wherein the linker group is an alkyl, vinyl, phenyl, alkynyl,
silyl, germyl, amine, ammonium, phosphine, phosphonium, ether,
thioether, borane, borate, alane, or aluminate group.
[0090] When at least one of R.sup.4 and R.sup.10 is a phenyl group
substituted at 3' and 5' positions, the phenyl group may also be
substituted at the 4' position, preferably with a substituent is
selected from (XR'.sub.n).sup.-, wherein X is a Group 14, 15, 16 or
17 heteroatom having an atomic weight of 13 to 79 (preferably N, O,
S, P, or Si) and R' is one of a hydrogen atom, halogen atom, a
C.sub.1-C.sub.10 alkyl group (such as methyl, ethyl, propyl, butyl,
pentyl, hexyl, octyl, nonyl, decyl or an isomer thereof), or a
C.sub.6-C.sub.10 aryl group and n is 0, 1, 2, or 3; preferably
(XR'.sub.n ).sup.-is --NR'.sub.2, --SR', --OR', --OSiR'.sub.3,
--SiR'.sub.3, or --PR'.sub.2, preferably (XR'.sub.n).sup.-is
--NR'.sub.2, --SR', --OR', --OSiR'.sub.3, or --PR'.sub.2,
preferably (XR'.sub.n).sup.-is --SR', --OR', or --OSiR'.sub.3,
preferably (XR'.sub.n).sup.-is --NR'.sub.2 or --PR'.sub.2, or
preferably (XR'.sub.n).sup.-is --OR' m preferably where R' is a
C.sub.1-C.sub.10 alkyl group, particularly a methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy, iso-butoxy, sec-butoxy, or
t-butoxy group, most particularly methoxy.
[0091] Preferred catalyst compounds include one or more of
rac-dimethylsilyl (4-o-biphenyl-2-n-hexyl-indenyl)
(2-methyl-4-(3',5'-di-tert-butyl-4'-methoxy-phenyl)-indenyl)
zirconium dichloride (MCN1 in Table 1), rac-dimethylsilyl
bis(4-o-biphenyl-2-n-butyl-indenyl) zirconium dichloride (MCN2 in
Table 1) and rac-dimethylsilyl (4-o-biphenyl-2-n-butyl indenyl)
(4-(3',5'-di-tert-butyl-4'-methoxyphenyl)-2-methyl-1,5,6,7-tetrahydro-s-i-
ndacenyl) zirconium dichloride (MCN8 in Table 1).
[0092] In another aspect, M is Hf, Ti and/or Zr, particularly Hf
and/or Zr, particularly Zr.
[0093] Suitable radicals for the each of the groups R.sup.1,
R.sup.3,R.sup.5, R.sup.6, R.sup.7, R.sup.9, R.sup.11, R.sup.12,
R.sup.13, and R.sup.14 are selected from hydrogen or hydrocarbyl
radicals including methyl, ethyl, ethenyl, and all isomers
(including cyclics such as cyclohexyl) of propyl, butyl, pentyl,
hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, propenyl,
butenyl, and from halocarbyls and all isomers of halocarbyls
including perfluoropropyl, perfluorobutyl, perfluoroethyl,
perfluoromethyl, and from substituted hydrocarbyl radicals and all
isomers of substituted hydrocarbyl radicals including
trimethylsilylpropyl, trimethylsilylmethyl, trimethylsilylethyl,
and from phenyl, and all isomers of hydrocarbyl substituted phenyl
including methylphenyl, dimethylphenyl, trimethylphenyl,
tetramethylphenyl, pentamethylphenyl, diethylphenyl,
triethylphenyl, propylphenyl, dipropylphenyl, tripropylphenyl,
dimethylethylphenyl, dimethylpropylphenyl, dimethylbutylphenyl,
dipropylmethylphenyl, and the like; from all isomers of halo
substituted phenyl (where halo is, independently, fluoro, chloro,
bromo and iodo) including halophenyl, dihalophenyl, trihalophenyl,
tetrahalophenyl, and pentahalophenyl; and from all isomers of halo
substituted hydrocarbyl substituted phenyl (where halo is,
independently, fluoro, chloro, bromo and iodo) including
halomethylphenyl, dihalomethylphenyl, (trifluoromethyl)phenyl,
bis(triflouromethyl)phenyl; and from all isomers of benzyl, and all
isomers of hydrocarbyl substituted benzyl including methylbenzyl,
dimethylbenzyl. Either or both of R.sub.5 and R.sub.6 and R.sub.11
and R.sub.12 may optionally join together to form a ring
structure.
[0094] Each X may independently be selected from the group
consisting of hydrocarbyl radicals having from 1 to 20 carbon
atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides,
dienes, amines, phosphines, ethers, and a combination thereof, and
two X may form a part of a fused ring or a ring system.
[0095] Suitable examples for X include chloride, bromide, fluoride,
iodide, hydride, and C.sub.1 to C.sub.20 hydrocarbyls, preferably
methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, benzyl, and
all isomers thereof, or two X together are selected from C.sub.4 to
C.sub.10 dienes, preferably butadiene, methylbutadiene, pentadiene,
methylpentadiene, dimethylpentadiene, hexadiene, methylhexadiene,
dimethylhexadiene, or from C.sub.1 to C.sub.10 alkylidenes,
preferably methylidene, ethylidene, propylidene, or from C.sub.3 to
C.sub.10 alkyldiyls, preferably propandiyl, butandiyl, pentandiyl,
and hexandiyl. In particular aspects, X is chloride or methyl.
[0096] T may be selected from R'.sub.2C, R'.sub.2Si, R'.sub.2Ge,
R'.sub.2CCR'.sub.2, R'.sub.2CCR'.sub.2CR'.sub.2, R'C.dbd.CR',
R'C.dbd.CR'CR'.sub.2, R'.sub.2CSiR'.sub.2, R'.sub.2SiSiR'.sub.2,
R'.sub.2CSiR'.sub.2CR'.sub.2, R'.sub.2SiCR'.sub.2SiR'.sub.2,
R'C.dbd.CR'SiR'.sub.2, R'.sub.2CGeR'.sub.2, R'.sub.2GeGeR'.sub.2,
R'.sub.2CGeR'.sub.2CR'.sub.2, R'.sub.2GeCR'.sub.2GeR'.sub.2,
R'.sub.2SiGeR'.sub.2, R'C.dbd.CR'GeR'.sub.2, R'B, R'.sub.2C--BR',
R'.sub.2C--BR'--CR'.sub.2, R'N, R'.sub.2C--NR',
R'.sub.2C--NR'--CR'.sub.2, R'P, R'.sub.2C--PR', and
R'.sub.2C--PR'--CR'.sub.2 where each R' is independently hydrogen,
hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted
halocarbyl, silylcarbyl, or germylcarbyl, and two or more R' on the
same atom or on adjacent atoms may join together to form a
substituted or unsubstituted, saturated, partially unsaturated, or
aromatic cyclic or polycyclic substituent.
[0097] Suitable examples for T may include dihydrocarbylsilylenes
including dimethylsilylene, diethylsilylene, dipropylsilylene,
dibutylsilylene, dipentylsilylene, dihexylsilylene,
methylphenylsilylene, diphenylsilylene, dicyclohexylsilylene,
methylcyclohexylsilylene, dibenzylsilylene, tetramethyldisilylene,
cyclotrimethylenesilylene, cyclotetramethylenesilylene,
cyclopentamethylenesilylene, divinylsilylene, and
tetramethyldisiloxylene; dihydrocarbylgermylenes including
dimethylgermylene, diethylgermylene, dipropylgermylene,
dibutylgermylene, methylphenylgermylene, diphenylgermylene,
dicyclohexylgermylene, methylcyclohexylgermylene,
cyclotrimethylenegermylene, cyclotetramethylenegermylene, and
cyclopentamethylenegermylene; carbylenes and carbdiyls including
methylene, dimethylmethylene, diethylmethylene, dibutylmethylene,
dipropylmethylene, diphenylmethylene, ditolylmethylene,
di(butylphenyl)methylene, di(trimethylsilylphenyl)methylene,
dibenzylmethylene, cyclotetramethylenemethylene,
cyclopentamethylenemethylene, ethylene, methylethylene,
dimethylethylene, trimethylethylene, tetramethylethylene,
cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene,
propanediyl, methylpropanediyl, dimethylpropanediyl,
trimethylpropanediyl, tetramethylpropanediyl,
pentamethylpropanediyl, hexamethylpropanediyl, vinylene, and
ethene-1,1-diyl; boranediyls including methylboranediyl,
ethylboranediyl, propylboranediyl, butylboranediyl,
pentylboranediyl, hexylboranediyl, cyclohexylboranediyl, and
phenylboranediyl; and combinations thereof including
dimethylsilylmethylene, diphenylsilylmethylene,
dimethylsilylethylene, methylphenylsilylmethylene.
[0098] In particular aspects, T is CH.sub.2, CH.sub.2CH.sub.2,
C(CH.sub.3).sub.2, SiMe.sub.2, SiPh.sub.2, SiMePh,
Si(CH.sub.2).sub.3, Si(CH.sub.2).sub.4, Si(Me.sub.3SiPh).sub.2, or
Si(CH.sub.2).sub.5.
[0099] T may also be represented by the formula R.sup.a.sub.2J,
where J is C, Si, or Ge, and each R.sup.a is, independently,
hydrogen, halogen, C.sub.1 to C.sub.20 hydrocarbyl, or C.sub.1 to
C.sub.20 substituted hydrocarbyl, and two R.sup.a can form a cyclic
structure including aromatic, partially saturated, or saturated
cyclic or fused ring system.
[0100] In a preferred embodiment of the invention, T is represented
by the formula, (R*.sub.2G).sub.g, where each G is C, Si, or Ge, g
is 1 or 2, and each R* is, independently, hydrogen, halogen,
C.sub.1 to C.sub.20 hydrocarbyl or a C.sub.1 to C.sub.20
substituted hydrocarbyl, and two or more R* can form a cyclic
structure including aromatic, partially saturated, or saturated
cyclic or fused ring system.
[0101] The racemic/meso ratio of the MCN catalyst compound may be
50:1 or greater, 40:1 or greater, 30:1 or greater, 20:1 or greater,
15:1 or greater, 10:1 or greater, 7:1 or greater, or 5:1 or
greater.
[0102] The MCN catalyst compound may comprise greater than 55 mol %
of the racemic isomer, greater than 60 mol % of the racemic isomer,
greater than 65 mol % of the racemic isomer, greater than 70 mol %
of the racemic isomer, greater than 75 mol % of the racemic isomer,
greater than 80 mol % of the racemic isomer, greater than 85 mol %
of the racemic isomer, greater than 90 mol % of the racemic isomer,
greater than 92 mol % of the racemic isomer, greater than 95 mol %
of the racemic isomer, greater than 98 mol % of the racemic isomer,
based on the total amount of the racemic and meso isomer (if any)
formed. In some aspects, the MCN catalyst compound consists
essentially of the racemic isomer.
[0103] Amounts of rac and meso isomers are determined by proton
NMR. .sup.1H NMR data are collected at 23.degree. C. in a 5 mm
probe using a 400 MHz Bruker spectrometer with deuterated methylene
chloride or deuterated benzene. Data is recorded using a maximum
pulse width of 45.degree., 8 seconds between pulses and signal
averaging 16 transients. The spectrum is normalized to protonated
methylene chloride in the deuterated methylene chloride, which is
expected to show a peak at 5.32 ppm.
[0104] In a preferred embodiment of the invention, one catalyst
compound is used, e.g., the catalyst compounds are not different.
For purposes of this invention one metallocene catalyst compound is
considered different from another if they differ by at least one
atom. For example "bisindenyl zirconium dichloride" is different
from (indenyl)(2-methylindenyl) zirconium dichloride" which is
different from "(indenyl)(2-methylindenyl) hafnium dichloride."
Catalyst compounds that differ only by isomer are considered the
same for purposes if this invention, e.g.,
rac-dimethylsilylbis(2-methyl 4-phenyl)hafnium dimethyl is
considered to be the same as meso-dimethylsilylbis(2-methyl
4-phenyl)hafnium dimethyl.
[0105] Additionally, two or more different MCN catalyst compounds
may be present in the catalyst system used herein. For example, two
or more different MCN catalyst compounds may be present in the
reaction zone where the process(es) described herein occur. When
two MCN catalyst compounds are used in one reactor as a mixed
catalyst system, the two compounds should be chosen such that the
two are compatible. A simple screening method such as by .sup.1H or
.sup.13C NMR, known to those of ordinary skill in the art, can be
used to determine which MCN catalyst compounds are compatible.
[0106] The transition metal compounds (pre-catalysts) may be used
in any ratio. Preferred molar ratios of (A) transition metal
compound to (B) transition metal compound fall within the range of
(A:B) 1:1000 to 1000:1, alternatively 1:100 to 500:1, alternatively
1:10 to 200:1, alternatively 1:1 to 100:1, and alternatively 1:1 to
75:1, and alternatively 5:1 to 50:1. The particular ratio chosen
will depend on the exact pre-catalysts chosen, the method of
activation, and the end product desired. In a particular
embodiment, when using the two pre-catalysts, where both are
activated with the same activator, useful mole percents, based upon
the molecular weight of the pre-catalysts, are 10 to 99.9% A to 0.1
to 90% B, alternatively 25 to 99% A to 0.5 to 50% B, alternatively
50 to 99% A to 1 to 25% B, and alternatively 75 to 99% A to 1 to
10% B.
[0107] Methods to Prepare the Catalyst Compounds: Generally, the
MCN catalyst compounds disclosed herein may be synthesized as shown
below where (i) is a deprotonation via a metal salt of alkyl anion
(e.g., .sup.nBuLi) to form an indenide; (ii) is a reaction of
indenide with an appropriate bridging precursor (e.g.,
Me.sub.2SiCl.sub.2); (iii) is a reaction of the above product with
AgOTf; (iv) is a reaction of the above triflate compound with
another equivalent of indenide; (v) is a double deprotonation via
an alkyl anion (e.g., .sup.nBuLi) to form a dianion; and (vi) is a
reaction of the dianion with a metal halide (e.g., ZrCl.sub.4). The
final products are obtained by recrystallization of the crude
solids.
##STR00004##
[0108] MCN catalyst compounds useful herein include:
rac-dimethylsilyl (4-o-biphenyl-2-n-hexyl-indenyl)
(2-methyl-4-(3',5'-di-tert-butyl-4'-methoxy-phenyl)-indenyl)
zirconium dichloride (MCN1 in Table 1), rac-dimethylsilyl
bis(4-o-biphenyl-2-n-butyl-indenyl) zirconium dichloride (MCN2 in
Table 1) and rac-dimethylsilyl (4-o-biphenyl-2-n-butyl indenyl)
(4-(3',5'-di-tert-butyl-4'-methoxyphenyl)-2-methyl-1,5,6,7-tetrahydro-s-i-
ndacenyl) zirconium dichloride (MCN8 in Table 1), etc.
[0109] Support: The catalyst systems comprise inert, porous solid
particles as a support to which the catalyst precursor compound
and/or activator may be anchored, bound, adsorbed or the like. The
support material comprises an inorganic oxide in a finely divided
form. Suitable inorganic oxide materials for use in MCN catalyst
systems herein include Groups 2, 4, 13, and 14 metal oxides, such
as silica, alumina, magnesia, titania, zirconia, and the like, and
mixtures thereof. Also, combinations of these support materials may
be used, for example, silica-chromium, silica-alumina,
silica-titania, and the like.
[0110] The support preferably comprises silica, e.g., amorphous
silica, which may include a hydrated surface presenting hydroxyl or
other groups which can be deprotonated to form reactive sites to
anchor activators and/or catalyst precursors. Other porous support
materials may optionally be present with the silica as a
co-support, for example, talc, other inorganic oxides, zeolites,
clays, organoclays, or any other organic or inorganic support
material and the like, or mixtures thereof. Silicas which may be
suitable are commercially available under the trade designations PD
14024 (PQ Corporation), D70-120A (Asahi Glass Co., Ltd. or AGC
Chemicals Americas, Inc.), and the like.
[0111] When a silica support is referred to herein, the silica
support in raw form comprises at least 60 wt %, 70 wt %, 80 wt %,
90 wt %, 95 wt %, 98 wt %, or 99 wt % or more of silica. The silica
support may comprise up to 5 wt %, 10 wt %, 20 wt %, 30 wt %, or 40
wt % of another compound. The other compound may be any other
support material discussed herein. The other compound may be a
titanium, aluminum, boron, magnesium, or mixtures thereof.
Additionally, the other compound may be a talc, other inorganic
oxide, zeolite, clay, organoclay, or mixtures thereof. The silica
support may also not include any substantial amount of any other
compound, i.e., the silica support comprises less than 5 wt %, 1 wt
%, 0.5 wt %, 0.2 wt %, or less of any other compound.
[0112] The support should be dry, that is, free of absorbed water.
Drying of the support may be effected by heating or calcining above
about 100.degree. C., e.g., from about 100.degree. C. to about
1000.degree. C., preferably at least about 200.degree. C. The
silica support may be heated to at least 130.degree. C., about
130.degree. C. to about 850.degree. C., or about 200.degree. C. to
about 600.degree. C. for a time of 1 minute to about 100 hours,
e.g., from about 12 hours to about 72 hours, or from about 24 hours
to about 60 hours. The calcined support material may comprise at
least some groups reactive with an organometallic compound, e.g.,
reactive hydroxyl (OH) groups to produce the supported catalyst
systems of this invention.
[0113] The support may have an average surface area of from about
400 to 800 m.sup.2/g support and an average pore diameter of from
about 60 to 200 Angstrom. The average surface area may range from a
low of about 400, 500, 530, 540, 550, or 600 m.sup.2/g support to a
high of about 600, 650, 700, 750, or 800 m.sup.2/g support,
including any combination of any upper or lower value disclosed
herein. The average pore diameter may range from a low of about 60,
70, 80, 90, 100, or 110 Angstrom to a high of about 120, 130, 150,
180, or 200 Angstrom, including any combination of any upper or
lower value disclosed herein.
[0114] The support may have an average pore volume of from about
0.5 to 2.5 ml/g support. The average pore volume may range from a
low of about 0.5, 0.7, 1.0, 1.1, 1.3, or 1.4 ml/g support to a high
of about 1.5, 1.6, 1.8, 2.0, or 2.5 ml/g support, including any
combination of any upper or lower value disclosed herein. The
average pore volume may be about 0.5 ml/g support, about 1.0 ml/g
support, about 1.5 ml/g support, or about any value disclosed
herein.
[0115] The support may have an average particle size of from about
20 to 200 micrometers. The average particle size may range from a
low of about 20, 30, 50, 70, or 80 to a high of about 80, 90, 100,
110, 130, or 200 micrometers, including any combination of any
upper or lower value disclosed herein.
[0116] At least 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%,
85% or even more of the incremental pore volume in the support may
be comprised of pores having a pore diameter larger than about 100,
125, or 150 Angstrom, and optionally smaller than about 1000, 900,
800 Angstrom, including any combination of numbers disclosed
herein. Additionally, less than 20%, 15%, 10%, 5%, 2.5% or less of
the incremental pore volume may be comprised of pores having a pore
diameter in the range of about 1000 Angstrom or more, about 900
Angstrom or more, or about 800 Angstrom or more.
[0117] The support may comprise agglomerates of a plurality of
primary particles, the support or agglomerates preferably having an
average particle size of at least 50 .mu.m, a surface area less
than 1000 m.sup.2/g support, or a combination thereof. The
agglomerates may be at least partially encapsulated. The
agglomerates may typically have an overall size range of 1-300
.mu.m (e.g., 30-200 .mu.m), the primary particles a size range of
0.001-50 .mu.m (e.g., 50-400 nm or 1-50 .mu.m), and the elementary
particles a size range of 1-400 nm (e.g., 5-40 nm). The
agglomerates may be created through spray drying or another
process. As used herein, "spray dried" refers to metal oxide such
as silica obtained by expanding a sol in such a manner as to
evaporate the liquid from the sol, e.g., by passing the silica sol
through a jet or nozzle with a hot gas. Alternatively, the porous
support does not comprise agglomerates.
[0118] The supports disclosed herein enable higher activator (e.g.,
aluminoxane) loadings than what has conventionally been possible
with MCN catalyst compounds. For example, the aluminoxane loading
on the porous silica support may be greater than about 9.0, 9.5,
10, 12, 14, or 18 mmol Al/g support. The aluminoxane loading may
range from a low of about 9.0, 9.5, 10, 11, 12, 13, 14, 15, or 16
mmol Al/g support to a high of about 12, 14, 16, 18, or 20 mmol
Al/g support, including any combination of any upper or lower value
disclosed herein.
[0119] For purposes herein, the term "aluminoxane loading" is the
amount of aluminoxane in the silica supported aluminoxane that is
adhered to silica particles. The aluminoxane may be adhered within
the outer or inner pores of the particles, adhered to the surface
of the particles, or otherwise adhered to the particles.
Aluminoxane loading may be represented as mmol Al/g silica.
[0120] Supportation: The support may be treated with an
organometallic compound to react with deprotonated reactive sites
on the support surface. In general the support is treated first
with an organometallic activator such as MAO, and then the
supported activator is treated with the MCN catalyst compound.
Alternatively, the MCN catalyst compound could be loaded on the
support first, followed by contact with the other catalyst system
components.
[0121] The support, having reactive surface groups especially after
calcining, may be slurried in a non-polar solvent and contacted
with the organometallic compound (activator in this example),
preferably dissolved in the solvent, preferably for a period of
time in the range of from about 0.5 hours to about 24 hours, from
about 2 hours to about 16 hours, or from about 4 hours to about 8
hours. Suitable non-polar solvents are materials in which, other
than the support and its adducts, all of the reactants used herein,
i.e., the activator, and the MCN catalyst compound, are at least
partially soluble and which are liquid at reaction temperatures.
Preferred non-polar solvents are alkanes, such as isopentane,
hexane, n-heptane, octane, nonane, and decane, although a variety
of other materials including cycloalkanes, such as cyclohexane,
aromatics, such as benzene, toluene, and ethylbenzene, may also be
employed.
[0122] The supported activator may optionally be treated with
another organometallic compound which is also selected as the
scavenger, preferably a metal alkyl such as an aluminum alkyl, to
scavenge any hydroxyl or other reactive species that may be exposed
by or otherwise remaining after treatment with the first
organometallic compound. Useful metal alkyls which may be used may
have the general formula R.sub.n-M, wherein R is C.sub.1-C.sub.40
hydrocarbyl such as C.sub.1-C.sub.12 alkyl, M is a metal, and n is
equal to the valence of M, and may include oxophilic species such
as diethyl zinc and aluminum alkyls, such as, for example,
trimethylaluminum, triethylaluminum, triisobutylaluminum,
tri-n-hexylaluminum, tri-n-octylaluminum and the like, including
combinations thereof. The supported activator may also be generated
in situ.
[0123] Activators: Activators are compounds used to activate any
one of the catalyst precursor compounds described above by
converting the neutral catalyst precursor compound to a
catalytically active catalyst compound cation. Preferred activators
include aluminoxane compounds, including modified aluminoxane
compounds.
[0124] Aluminoxanes are generally oligomeric, partially hydrolyzed
aluminum alkyl compounds containing --Al(R1)--O-- sub-units, where
R1 is an alkyl group, and may be produced by the hydrolysis of the
respective trialkylaluminum compound. Examples of aluminoxane
activators include methylaluminoxane (MAO), ethylaluminoxane,
butylaluminoxane, isobutylaluminoxane, modified MAO (MMAO),
halogenated MAO where the MAO may be halogenated before or after
MAO supportation, dialkylaluminum cation enhanced MAO, surface
bulky group modified MAO, and the like. MMAO may be produced by the
hydrolysis of trimethylaluminum and a higher trialkylaluminum such
as triisobutylaluminum. Mixtures of different aluminoxanes may also
be used as the activator(s).
[0125] There are a variety of methods for preparing aluminoxanes
suitable for use in the present invention, non-limiting examples of
which are described in U.S. Pat. No. 4,665,208, U.S. Pat. No.
4,952,540, U.S. Pat. No. 5,041,584, U.S. Pat. No. 5,091,352, U.S.
Pat. No. 5,206,199, U.S. Pat. No. 5,204,419, U.S. Pat. No.
4,874,734, U.S. Pat. No. 4,924,018, U.S. Pat. No. 4,908,463, U.S.
Pat. No. 4,968,827, U.S. Pat. No. 5,308,815, U.S. Pat. No.
5,329,032, U.S. Pat. No. 5,248,801, U.S. Pat. No. 5,235,081, U.S.
Pat. No. 5,157,137, U.S. Pat. No. 5,103,031, U.S. Pat. No.
5,391,793, U.S. Pat. No. 5,391,529, U.S. Pat. No. 5,693,838, U.S.
Pat. No. 5,731,253, U.S. Pat. No. 5,731,451, U.S. Pat. No.
5,744,656, U.S. Pat. No. 5,847,177, U.S. Pat. No. 5,854,166, U.S.
Pat. No. 5,856,256 and U.S. Pat. No. 5,939,346 and European
publications EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and
EP-B 1-0 586 665, and PCT publications WO 94/10180 and WO 99/15534;
halogenated MAO are described in U.S. Pat. No. 7,960,488; U.S. Pat.
No. 7,355,058; and U.S. Pat. No. 8,354,485; dialkylaluminum cation
enhanced MAO are described in US 2013/0345376; and surface bulky
group modified supported MAO are described in U.S. Pat. No.
8,895,465, all of which are herein fully incorporated by
reference.
[0126] Optional Scavengers or Co-Activators: In addition to the
activator compounds, scavengers or co-activators may be used.
Suitable co-activators may be selected from the group consisting
of: trialkylaluminum, dialkylmagnesium, alkylmagnesium halide, and
dialkylzinc. Aluminum alkyl or organoaluminum compounds which may
be utilized as scavengers or co-activators include, for example,
trimethylaluminum, triethylaluminum, triisobutylaluminum,
tri-n-hexylaluminum, tri-n-octylaluminum, and the like. Other
oxophilic species, such as diethyl zinc may be used. As mentioned
above, the organometallic compound used to treat the calcined
support material may be a scavenger or co-activator, or may be the
same as or different from the scavenger or co-activator. In an
embodiment, the co-activator is selected from the group consisting
of: trimethylaluminum, triethylaluminum, triisobutylaluminum,
tri-n-octylaluminum, trihexylaluminum, and diethylzinc (alternately
the group consisting of: trimethylaluminum, triethylaluminum,
triisobutylaluminum, trihexylaluminum, tri-n-octylaluminum,
dimethylmagnesium, diethylmagnesium, dipropylmagnesium,
diisopropylmagnesium, dibutyl magnesium, diisobutylmagnesium,
dihexylmagnesium, dioctylmagnesium, methylmagnesium chloride,
ethylmagnesium chloride, propylmagnesium chloride,
isopropylmagnesium chloride, butyl magnesium chloride,
isobutylmagnesium chloride, hexylmagnesium chloride, octylmagnesium
chloride, methylmagnesium fluoride, ethylmagnesium fluoride,
propylmagnesium fluoride, isopropylmagnesium fluoride, butyl
magnesium fluoride, isobutylmagnesium fluoride, hexylmagnesium
fluoride, octylmagnesium fluoride, dimethylzinc, diethylzic,
dipropylzinc, and dibutylzinc).
[0127] Chain Transfer Agents: One or more chain transfer agent
("CTA") may be used in the polymerization processes disclosed
herein. The CTA can be any desirable chemical compound such as
those disclosed in WO 2007/130306. Preferably, the CTA is selected
from Group 2, 12, or 13 alkyl or aryl compounds; preferably zinc,
magnesium or aluminum alkyls or aryls; preferably where the alkyl
is a C.sub.1 to C.sub.30 alkyl, alternately a C.sub.2 to C.sub.20
alkyl, alternately a C.sub.3 to C.sub.12 alkyl, typically selected
independently from methyl, ethyl, propyl, butyl, isobutyl,
tertbutyl, pentyl, hexyl, cyclohexyl, phenyl, octyl, nonyl, decyl,
undecyl, and dodecyl; e.g., dialkyl zinc compounds, where the alkyl
is selected independently from methyl, ethyl, propyl, butyl,
isobutyl, tertbutyl, pentyl, hexyl, cyclohexyl, and phenyl, where
di-ethylzinc is particularly preferred; or e.g., trialkyl aluminum
compounds, where the alkyl is selected independently from methyl,
ethyl, propyl, butyl, isobutyl, tertbutyl, pentyl, hexyl,
cyclohexyl, and phenyl; or e.g., diethyl aluminum chloride,
diisobutylaluminum hydride, diethylaluminum hydride,
di-n-octylaluminum hydride, dibutylmagnesium, diethylmagnesium,
dihexylmagnesium, and triethylboron.
[0128] Useful CTAs are typically present at from 10 or 20 or 50 or
100 equivalents to 600 or 700 or 800 or 1000 equivalents relative
to the catalyst component. Alternately the CTA is preset at a
catalyst complex-to-CTA molar ratio of from about 1:3000 to 10:1;
alternatively 1:2000 to 10:1; alternatively 1:1000 to 10:1;
alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1;
alternatively 1:200 to 1:1; alternatively 1:100 to 1:1;
alternatively 1:50 to 1:1; or/and alternatively 1:10 to 1:1.
[0129] Monomers: Monomers useful herein include substituted or
unsubstituted C.sub.2 to C.sub.40 alpha olefins, preferably C.sub.2
to C.sub.20 alpha olefins, preferably C.sub.2 to C.sub.12 alpha
olefins, preferably ethylene, propylene, butene, pentene, hexene,
heptene, octene, nonene, decene, undecene, dodecene, and isomers
thereof. The monomer may comprise propylene with optional
co-monomer(s) comprising one or more of ethylene or C.sub.4 to
C.sub.40 olefins, preferably C.sub.4 to C.sub.20 olefins, or
preferably C.sub.6 to C.sub.12 olefins. The C.sub.4 to C.sub.40
olefin monomers may be linear, branched, or cyclic. The C.sub.4 to
C.sub.40 cyclic olefins may be strained or unstrained, monocyclic
or polycyclic, and may optionally include heteroatoms and/or one or
more functional groups. Additionally, the monomer may be propylene
with no co-monomer is present.
[0130] Exemplary C.sub.2 to C.sub.40 olefin monomers and optional
co-monomers include ethylene, propylene, butene, pentene, hexene,
heptene, octene, nonene, decene, undecene, dodecene, norbornene,
norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene,
cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene,
7-oxanorbornadiene, substituted derivatives thereof, and isomers
thereof, preferably hexene, heptene, octene, nonene, decene,
dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene,
1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene,
dicyclopentadiene, norbornene, norbornadiene, and their respective
homologs and derivatives, preferably norbornene, norbornadiene, and
dicyclopentadiene.
[0131] One or more dienes may be present in the polymer produced
herein at up to 10 wt %, preferably at 0.00001 to 1.0 wt %,
preferably 0.002 to 0.5 wt %, even more preferably 0.003 to 0.2 wt
%, based upon the total weight of the composition. In some
embodiments 500 ppm or less of diene is added to the
polymerization, preferably 400 ppm or less, preferably or 300 ppm
or less. In other embodiments, at least 50 ppm of diene is added to
the polymerization, or 100 ppm or more, or 150 ppm or more.
[0132] Diolefin monomers useful in this invention include any
hydrocarbon structure, preferably C.sub.4 to C.sub.30, having at
least two unsaturated bonds, wherein at least two of the
unsaturated bonds are readily incorporated into a polymer by either
a stereospecific or a non-stereospecific catalyst(s). The diolefin
monomers may be selected from alpha, omega-diene monomers (i.e.,
di-vinyl monomers). The diolefin monomers may be linear di-vinyl
monomers, most preferably those containing from 4 to 30 carbon
atoms. Examples of preferred dienes include butadiene, pentadiene,
hexadiene, heptadiene, octadiene, nonadiene, decadiene,
undecadiene, dodecadiene, tridecadiene, tetradecadiene,
pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene,
nonadecadiene, icosadiene, heneicosadiene, docosadiene,
tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene,
heptacosadiene, octacosadiene, nonacosadiene, triacontadiene,
particularly preferred dienes include 1,6-heptadiene,
1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene,
1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and low
molecular weight polybutadienes (Mw less than 1000 g/mol).
Preferred cyclic dienes include cyclopentadiene, vinylnorbornene,
norbornadiene, ethylidene norbornene, divinylbenzene,
dicyclopentadiene, or higher ring containing diolefins with or
without substituents at various ring positions.
[0133] The polymerization or copolymerization may be carried out
using olefins such as ethylene, propylene, 1-butene, 1-hexene,
4-methyl-l-pentene, and 1-octene, vinylcyclohexane, norbornene and
norbornadiene. In particular, propylene and ethylene are
polymerized.
[0134] Preferably, the co-monomer(s) are present in the final
propylene polymer composition at less than 50 mol %, preferably
from 0.5 to 45 mol %, preferably from 1 to 30 mol %, preferably
from 3 to 25 mol %, preferably from 5 to 20 mol %, preferably from
7 to 15 mol %, with the balance of the copolymer being made up of
the main monomer (e.g., propylene), based on the molecular.
[0135] Polymerization: Polymerization processes using the catalyst
systems disclosed herein can be carried out in any manner known in
the art. Any suspension, homogeneous, bulk, solution, slurry, or
gas phase polymerization process known in the art can be used. Such
processes can be run in a batch, semi-batch, or continuous mode.
Homogeneous polymerization processes and slurry processes are
useful. (A homogeneous polymerization process is defined to be a
process where at least 90 wt % of the product is soluble in the
reaction media.) A bulk homogeneous process is also useful. (A bulk
process is defined to be a process where monomer concentration in
all feeds to the reactor is 70 volume % or more.) Alternately, no
solvent or diluent is present or added in the reaction medium,
(except for the small amounts used as the carrier for the catalyst
system or other additives, or amounts typically found with the
monomer; e.g., propane in propylene). In another embodiment, the
process is a slurry process. As used herein, the term "slurry
polymerization process" means a polymerization process where a
supported catalyst is employed and monomers are polymerized on the
supported catalyst particles. At least 95 wt % of polymer products
derived from the supported catalyst are in granular form as solid
particles (not dissolved in the diluent).
[0136] Suitable diluents/solvents for polymerization include
non-coordinating, inert liquids. Examples include straight and
branched-chain hydrocarbons, such as isobutane, butane, pentane,
isopentane, hexanes, isohexane, heptane, octane, dodecane, and
mixtures thereof; cyclic and alicyclic hydrocarbons, such as
cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane,
and mixtures thereof, such as can be found commercially
(Isopar.TM.); perhalogenated hydrocarbons, such as perfluorinated
C.sub.4-10 alkanes, chlorobenzene, and aromatic and
alkylsubstituted aromatic compounds, such as benzene, toluene,
mesitylene, and xylene. Suitable solvents also include liquid
olefins which may act as monomers or comonomers including ethylene,
propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-l-pentene,
4-methyl-l-pentene, 1-octene, 1-decene, and mixtures thereof. In a
preferred embodiment, aliphatic hydrocarbon solvents are used as
the solvent, such as isobutane, butane, pentane, isopentane,
hexanes, isohexane, heptane, octane, dodecane, and mixtures
thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane,
cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures
thereof. In another embodiment, the solvent is not aromatic,
preferably aromatics are present in the solvent at less than 1 wt
%, preferably less than 0.5 wt %, preferably less than 0 wt % based
upon the weight of the solvents.
[0137] Polymerizations can be run at any temperature and/or
pressure suitable to obtain the desired ethylene polymers. Typical
temperatures and/or pressures include a temperature in the range of
from about 0.degree. C. to about 300.degree. C., preferably about
20.degree. C. to about 200.degree. C., preferably about 35.degree.
C. to about 150.degree. C., preferably from about 40.degree. C. to
about 120.degree. C., preferably from about 45.degree. C. to about
80.degree. C.; and a pressure in the range of from about 0.35 MPa
to about 10 MPa, preferably from about 0.45 MPa to about 6 MPa, or
preferably from about 0.5 MPa to about 4 MPa.
[0138] In a typical polymerization, the run time of the reaction is
up to 300 minutes, preferably in the range of from about 5 to 250
minutes, or preferably from about 10 to 120 minutes.
[0139] Hydrogen may be present in the polymerization reactor at a
partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), preferably
from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10
psig (0.7 to 70 kPa). Alternatively, hydrogen is not added to the
polymerization reactor; hydrogen may be present from other sources,
such as a hydrogen-generating catalyst, but none is added to the
reactor.
[0140] The activity of the catalyst may be at least 50 g/mmol/hour,
500 g/mmol/hour or more, 5000 g/mmol/hr or more, 50,000 g/mmol/hr
or more, 100,000 g/mmol/hr or more, 150,000 g/mmol/hr or more,
200,000 g/mmol/hr or more, 250,000 g/mmol/hr or more, 300,000
g/mmol/hr or more, or 350,000 g/mmol/hr or more.
[0141] Polymer Products: The processes described herein can produce
a variety of polymer products, including but not limited to
ethylene and propylene homopolymers and copolymers. The polymers
produced may be homopolymers of ethylene or propylene or copolymers
of ethylene preferably having from 0 to 25 mole % (alternately from
0.5 to 20 mole %, alternately from 1 to 15 mole %, preferably from
3 to 10 mole %) of one or more C3 to C20 olefin comonomer
(preferably C.sub.3 to C.sub.12 alpha-olefin, preferably propylene,
butene, hexene, octene, decene, dodecene, preferably propylene,
butene, hexene, octene), or are copolymers of propylene preferably
having from 0 to 25 mole % (alternately from 0.5 to 20 mole %,
alternately from 1 to 15 mole %, preferably from 3 to 10 mole %) of
one or more of C2 or C4 to C20 olefin comonomer (preferably
ethylene or C4 to C12 alpha-olefin, preferably ethylene, butene,
hexene, octene, decene, dodecene, preferably ethylene, butene,
hexene, octene).
[0142] The polymers may comprise polypropylene, for example, iPP,
highly isotactic polypropylene, sPP, hPP, and RCP. The
polypropylene polymer may also be heterophasic. The propylene
polymer may also be an impact copolymer (ICP). The ICP comprises a
blend of iPP, preferably with a T.sub.m of 120.degree. C. (DSC,
peak second melt) or more, with a propylene polymer with a glass
transition temperature (T.sub.g) of -30.degree. C. or less and/or
an ethylene polymer.
[0143] The polymers may comprise isotactic polypropylene having a
melting temperature, Tm, DSC peak second melt, of at least
151.degree. C., 152.degree. C., or 153.degree. C. or more. The
polymers may also comprise isotactic polypropylene having a melt
flow rate (MFR, ASTM D-1238, 2.16 kg and 230.degree. C.) of less
than about 0.4, 0.35, or 0.3 dg/min Additionally, the polymers may
comprise isotactic polypropylene having a molecular weight, Mw, of
at least 600, 1000, or 1400 kg/mol.
[0144] The polymers produced herein may be combined with one or
more additional polymers prior to being formed into a film, molded
part, or other article. Other useful polymers include polyethylene,
isotactic polypropylene, highly isotactic polypropylene,
syndiotactic polypropylene, random copolymer of propylene and
ethylene, and/or butene, and/or hexene, polybutene, ethylene vinyl
acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl
acrylate, copolymers of acrylic acid, polymethylmethacrylate or any
other polymers polymerizable by a high-pressure free radical
process, polyvinylchloride, polybutene-1, isotactic polybutene, ABS
resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM,
block copolymer, styrenic block copolymers, polyamides,
polycarbonates, PET resins, cross linked polyethylene, copolymers
of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers
such as polystyrene, poly-1 esters, polyacetal, polyvinylidine
fluoride, polyethylene glycols, and/or polyisobutylene.
[0145] The blends may be formed using conventional equipment and
methods, such as by dry blending the individual components and
subsequently melt mixing in a mixer, or by mixing the components
together directly in a mixer, such as, for example, a Banbury
mixer, a Haake mixer, a Brabender internal mixer, or a single or
twin-screw extruder, which may include a compounding extruder and a
side-arm extruder used directly downstream of a polymerization
process, which may include blending powders or pellets of the
resins at the hopper of the film extruder. Additionally, additives
may be included in the blend, in one or more components of the
blend, and/or in a product formed from the blend, such as a film,
as desired. Such additives are well known in the art, and can
include, for example: fillers; antioxidants (e.g., hindered
phenolics such as IRGANOX.TM.1010 or IRGANOX.TM.1076 available from
Ciba-Geigy); phosphites (e.g., IRGAFOS.TM.168 available from
Ciba-Geigy); anti-cling additives; tackifiers, such as polybutenes,
terpene resins, aliphatic and aromatic hydrocarbon resins, alkali
metal and glycerol stearates, and hydrogenated rosins; UV
stabilizers; heat stabilizers; anti-blocking agents; release
agents; anti-static agents; pigments; colorants; dyes; waxes;
silica; fillers; talc; and the like.
[0146] Impact Copolymers: The polymers produced herein can be used
in impact copolymers. The impact copolymer (ICP) can include a
polypropylene polymer produced herein and another polymer such as
an ethylene copolymer. The morphology is typically such that the
matrix phase is primarily the polypropylene polymer and the
dispersed phase can be primarily the ethylene copolymer phase.
[0147] The impact copolymer can have a total propylene content of
at least 75 wt %, at least 80 wt %, at least 85 wt %, at least 90
wt %, or at least 95 wt %, based on the weight of the impact
copolymer.
[0148] The impact copolymer can have a total comonomer content from
about 1 wt % to about 35 wt %, about 2 wt % to about 30 wt %, about
3 wt % to about 25 wt %, or about 5 wt % to about 20 wt %, based on
the total weight of the impact copolymer, with the balance being
propylene.
[0149] Preferred impact copolymers comprise iPP and ethylene
copolymer and typically have an ethylene copolymer (preferably
ethylene propylene copolymer) content from a low of about 5 wt %,
about 8 wt %, about 10 wt %, or about 15 wt % to a high of about 25
wt %, about 30 wt %, about 38 wt %, or about 42 wt %. For example,
the impact polymer can have an ethylene copolymer content of about
5 wt % to about 40 wt %, about 6 wt % to about 35 wt %, about 7 wt
% to about 30 wt %, or about 8 wt % to about 30 wt %.
[0150] In preferred impact copolymers comprising iPP and ethylene
copolymer, the impact copolymer can have a propylene content of the
ethylene copolymer component from a low of about 25 wt %, about 37
wt %, or about 46 wt % to a high of about 73 wt %, about 77 wt %,
or about 80 wt %, based on the based on a weight of the ethylene
copolymer. For example, the impact copolymer can have a propylene
content of the ethylene copolymer component from about 25 wt % to
about 80 wt %, about 10 wt % to about 75 wt %, about 35 wt % to
about 70 wt %, or at least 40 wt % to about 80 wt %, based on the
weight of the ethylene copolymer.
[0151] In preferred impact copolymers comprising iPP and ethylene
copolymer, the impact copolymer can have ratio of the intrinsic
viscosity (IV, ASTM D 1601 -135.degree. C. in decalin) of the
ethylene copolymer component to the intrinsic viscosity of the
polypropylene component from a low of about 0.5, about 1.5, about
3, or about 4 to a high of about 6, about 9, about 12, or about 15.
For example, the impact copolymer component can have a ratio of the
intrinsic viscosity of about 0.5 to about 15, about 0.75 to about
12, or about 1 to about 7.
[0152] The impact copolymer can have a propylene meso diads content
in the polypropylene component 90% or more, 92% or more, about 94%
or more, or about 96% or more. Polypropylene microstructure is
determined according to the `.sup.3C NMR procedure described in US
2008/0045638 at paragraph [0613].
[0153] The impact copolymer can have a weight average molecular
weight (Mw) from a low of about 20 kg/mol, about 50 kg/mol, about
75 kg/mol, about 150 kg/mol, or about 300 kg/mol to a high of about
600 kg/mol, about 900 kg/mol, about 1,300 kg/mol, or about 2,000
kg/mol. For example, the ethylene copolymer can have a Mw of about
50 kg/mol to about 3,000 kg/mol, about 100 kg/mol to about 2,000
kg/mol, or about 200 kg/mol to about 1,000 kg/mol.
[0154] The impact copolymer can have a melt flow rate (MFR) from
about 1 dg/min to about 300 dg/min, about 5 dg/min to about 150
dg/min, or about 10 dg/min to about 100 dg/min, or about 20 dg/min
to about 60 dg/min.
[0155] The impact copolymer can have a melting point (Tm, peak
second melt) from at least 100.degree. C. to about 175.degree. C.,
about 105.degree. C. to about 170.degree. C., about 110.degree. C.
to about 165.degree. C., or about 115.degree. C. to about
155.degree. C.
[0156] The impact copolymer can have a heat of fusion (H.sub.f, DSC
second heat) of 60 J/g or more, 70 J/g or more, 80 J/g or more, 90
J/g or more, about 95 J/g or more, or about 100 J/g or more.
[0157] The impact copolymer can have a 1% secant flexural modulus
from about 300 MPa to about 3,000 MPa, about 500 MPa to about 2,500
MPa, about 700 MPa to about 2,000 MPa, or about 900 MPa to about
1,500 MPa, as measured according to ASTM D 790 (A, 1.3 mm/min).
[0158] The impact copolymer can have a notched Izod impact strength
at 23.degree. C. of about 2.5 KJ/m.sup.2 or more, about 5
KJ/m.sup.2 or more, about 7.5 KJ/m.sup.2 or more, about 10
KJ/m.sup.2 or more, about 15 KJ/m.sup.2 or more, about 20
KJ/m.sup.2 or more, about 25 KJ/m.sup.2 or more, or about 50
KJ/m.sup.2 or more, as measured according to ASTM D 256 (Method A),
optionally to a high of about 30 KJ/m.sup.2, about 35 KJ/m.sup.2,
about 45 KJ/m.sup.2, about 55 KJ/m.sup.2, or about 65
KJ/m.sup.2.
[0159] The impact copolymer can have a Gardner impact strength at
-30.degree. C. from about 2 KJ/m.sup.2 to about 100 KJ/m.sup.2,
about 3 KJ/m.sup.2 to about 80 KJ/m.sup.2, or about 4 KJ/m.sup.2 to
about 60 KJ/m.sup.2, as measured according to ASTM D 5420 (GC).
[0160] The impact copolymer can have a heat deflection temperature
(HDT) of about 80.degree. C. or more, about 85.degree. C. or more,
about 90.degree. C. or more, or about 95.degree. C. or more, as
measured according to ASTM D 648 (0.45 MPa).
EXPERIMENTAL
[0161] Melt Flow Rate (MFR) was determined in accordance with ASTM
D-1238 Condition L under a load of 2.16 kg and at a temperature of
230.degree. C.
[0162] Mw, Mn, and MWD (Mw/Mn) were determined using a High
Temperature Gel Permeation Chromatograph (Polymer Laboratories),
equipped with a differential refractive index detector (DRI). Three
Polymer Laboratories PLgel 10 .mu.m Mixed-B columns are used. The
nominal flow rate is 1.0 ml/min, and the nominal injection volume
is 300 .mu.L. The various transfer lines, columns, and differential
refractometer (the DRI detector) are contained in an oven
maintained at 160.degree. C. Solvent for the experiment is prepared
by dissolving 6 grams of butylated hydroxytoluene as an antioxidant
in 4 liters of Aldrich reagent grade 1, 2, 4 trichlorobenzene
(TCB). The TCB mixture is then filtered through a 0.1 .mu.m Teflon
filter. The TCB is then degassed with an online degasser before
entering the GPC instrument. Polymer solutions are prepared by
placing dry polymer in glass vials, adding the desired amount of
TCB, then heating the mixture at 160.degree. C. with continuous
shaking for about 2 hours. All quantities are measured
gravimetrically. The injection concentration is from 0.5 to 2.0
mg/ml, with lower concentrations being used for higher molecular
weight samples. Prior to running each sample, the DRI detector is
purged. Flow rate in the apparatus is then increased to 1.0
ml/minute, and the DRI is allowed to stabilize for 8 hours before
injecting the first sample. The molecular weight is determined by
combining the universal calibration relationship with the column
calibration which is performed with a series of monodispersed
polystyrene (PS) standards. The MW is calculated at each elution
volume with following equation:
log M X = log ( K X / K PS ) a X + 1 + a PS + 1 a X + 1 log M PS
##EQU00001##
where the variables with subscript "X" stand for the test sample
while those with subscript "PS" stand for polystyrene. In this
method, a.sub.PS=0.67 and K.sub.PS=0.000175 while a.sub.X and
K.sub.X are obtained from published literature. Specifically, a and
K=0.695 and 0.000579 for ethylene polymer and 0.705 and 0.0002288
for propylene polymer. The concentration, c, at each point in the
chromatogram is calculated from the baseline-subtracted DRI signal,
I.sub.DRI, using the following equation:
C=K.sub.DRII.sub.DRI/(dn/dc)
where K.sub.DRI is a constant determined by calibrating the DRI,
and (dn/dc) is the refractive index increment for the system.
Specifically, dn/dc=0.109 for both propylene polymer and ethylene
polymer. The mass recovery is calculated from the ratio of the
integrated area of the concentration chromatography over elution
volume and the injection mass, which is equal to the pre-determined
concentration multiplied by injection loop volume. All molecular
weights are reported in g/mol unless otherwise noted. In the event
of conflict between the GPC-DRI procedure and the "Rapid GPC," the
GPC-DRI procedure immediately above shall be used. Further details
regarding methods of determining Mw, Mn, MWD are described in US
2006/0173123 pages 24-25, paragraphs [0334] to [0341].
[0163] Melting Temperature, T.sub.m, was measured by differential
scanning calorimetry ("DSC") using a DSC Q200 unit (TA
Instruments). The sample is first equilibrated at 25.degree. C. and
subsequently heated to 220.degree. C. using a heating rate of
10.degree. C./min (first heat). The sample is held at 220.degree.
C. for 3 min. The sample is subsequently cooled down to
-100.degree. C. with a constant cooling rate of 10.degree. C./min
(first cool). The sample is equilibrated at -100.degree. C. before
being heated to 220.degree. C. at a constant heating rate of
10.degree. C./min (second heat). The exothermic peak of
crystallization (first cool) is analyzed using the TA Universal
Analysis software and the corresponding to 10.degree. C./min
cooling rate is determined. The endothermic peak of melting (second
heat) is also analyzed using the TA Universal Analysis software and
the peak melting temperature (T.sub.m) corresponding to 10.degree.
C./min heating rate is determined.
[0164] 1% Secant Flexural Modulus was measured using an ISO 37-Type
3 bar, with a crosshead speed of 1.0 mm/min and a support span of
30.0 mm using an Instron machine according to ASTM D 790 (A, 1.0
mm/min).
[0165] Catalyst Synthesis: The following supported catalysts were
used in the examples. The chemical formulas for the MCN catalyst
compounds are provided in Table 1 below. Procedures for
synthesizing the catalyst compounds are also provided below.
[0166] Catalyst A: MCN1 supported on PD14024.
[0167] Catalyst B: MCN1 supported on D70-120A.
[0168] Catalyst C: MCN2 supported on PD14024.
[0169] Catalyst D (Comparative): MCN3 supported on PD14024.
[0170] Catalyst E (Comparative): MCN4 supported on PD14024.
[0171] Catalyst F (Comparative): MCN5 supported on PD14024.
[0172] Catalyst G: MCN8 supported on PD14024.
[0173] Catalyst H (Comparative): MCN6 supported on Davison 948
silica.
[0174] Catalyst I (Comparative): MCN7 supported on Davison 948
silica.
TABLE-US-00001 TABLE 1 MCN Catalyst Compounds ##STR00005## MCN1
##STR00006## MCN2 ##STR00007## MCN3 ##STR00008## MCN4 ##STR00009##
MCN5 ##STR00010## MCN6 ##STR00011## MCN7 ##STR00012## MCN8
MCN1 Synthesis:
[0175] 4-([1,1'-Biphenyl]-2-yl)-2-n-Hex-1H-indene: Two procedures
are provided for this synthesis, either being suitable. Procedure
1: A solution of compound
4-([1,1'-Biphenyl]-2-yl)-2-bromo-1H-indene (15 g, 43.2 mmol, 1
equiv.) and anhydrous toluene (150 mL) was treated with
bis(triphenylphosphine)palladium(II)-dichloride (3.5 g, 4.3 mmol,
0.1 equiv.). After stirring for 10 minutes, 2 M hexylmagnesium
bromide in diethyl ether (112 mL, 224.6 mmol, 5.2 equiv.) was added
dropwise. The reaction was heated at 60.degree. C. for 5 hours. The
reaction was cooled with an ice bath, acidified with 1NHCl to pH 3
and extracted with ethyl acetate (3.times.500 mL). The combined
organic layers were washed with saturated brine (800 mL), dried
over sodium sulfate, and concentrated under reduced pressure. The
residue was purified over silica gel (200 g) eluting with heptanes
to give the product (7 g, 46% yield) as a light yellow oil.
Procedure 2: In a glove box, n-hexylmagnesium bromide (34.7 mL, 2.0
M in diethyl ether, 69.4 mmol) was added to a solution of
4-([1,1'-Biphenyl]-2-yl)-2-bromo-1H-indene (20.0 g, 57.8 mmol) and
PdCl (dppf).DCM (2.30 g, 2.89 mmol) in 100 mL of THF. The reaction
was heated up to 40.degree. C. and stirred at this temperature for
10 hours. The reaction was cooled down to RT and the solvent was
evaporated. The residue was moved out the glove box and quenched
with 200 mL of water and the mixture was extracted with hexane (100
mL.times.2). The combined organic phases were dried over MgSO.sub.4
and concentrated in vacuo. The residue was purified by silica gel
chromatography (eluent: hexane) to get product as colorless oil
(19.52 g).
[0176] Lithium {1-[4-(3',5'-di-tert-4'-methoxybutylphenyl)-2-methyl
indenide]}: A precooled solution of
4-(3',5'-di-tert-butyl-4'-methoxyphenyl)-2-methyl-indene (15.0 g,
43.1 mmol) in diethyl ether (200 mL) was treated with .sup.nBuLi
(2.5 M in hexane, 18.1 mL, 45.3 mmol). The reaction was stirred at
RT for 15 hours. Then all volatiles were evaporated. The residue
was washed with pentane (10 mL) and dried under vacuum to yield a
white solid (15.15 g).
[0177] Chlorodimethyl [4-(3',5 '-di-tert-butyl-4
`-methoxyphenyl)-2-methyl-indenyl] silane: A precooled solution of
lithium 1-[4-(3',5'-di-tert-4'-methoxybutylphenyl)-2-methyl
indenidel (15.1 g, 42.8 mmol) in diethyl ether (100 mL) was treated
with Me.sub.2SiCl.sub.2 (27.4 g, 214.0 mmol), and the white slurry
was stirred at RT for 5 hours. All volatiles were evaporated under
reduced pressure. The residue was extracted with hexane (100
mL.times.2), and the combined filtrate was concentrated to dryness
under vacuum to give white foam (18.36 g).
[0178] Dimethylsilyl [4-(3',5
'-di-tert-butyl-4'-methoxyphenyl)-2-methyl-indenyl]
trifluoromethane-sulfonate: A solution of
chlorodimethyl[4-(3',5'-di-tert-butyl-4'-methoxyphenyl)-2-methyl-indenyl]-
silane (18.34 g, 41.7 mmol) in toluene (100 mL) was treated with
silver trifluoromethanesulfonate (11.2 g, 43.8 mmol) while
stirring. The white slurry was stirred at RT for 5 hours. Toluene
was removed under vacuum and the residue was extracted with hexane
(100 mL.times.2). The collected filtrate was concentrated under
vacuum to give colorless foam as the product (22.82 g).
[0179] Lithium [1-(4-o-Biphenyl)-2-hexyl-indenide]: A precooled
solution of 4-([1,1'-Biphenyl]-2-yl)-2-n-Hex-1H-indene (15.0 g,
42.6 mmol) in diethyl ether (100 mL) was treated with .sup.nBuLi
(2.5 M in hexane, 17.9 mL, 44.7 mmol). The reaction was stirred at
RT for 3 hours. Then all volatiles were evaporated. The residue was
washed with hexane (20mL.times.2) and dried under vacuum to yield a
white solid as the product (14.21 g).
[0180] (4-o-Biphenyl-2-hexyl-indenyl)
(4-(3',5'-di-tert-butyl-4'-methoxyphenyl)-2-methyl-indenyl)
dimethylsilane: A precooled solution of
dimethylsilyl[4-(3',5'-di-tert-butyl-4'-methoxyphenyl)-2-methyl-indenyl]
trifluoromethanesulfonate (22.73 g, 39.2 mmol) in diethyl ether
(100 mL) was treated with lithium [1-(4-o-biphenyl-2-hexyl
indenide)] (14.03 g, 39.2 mmol). The solution was stirred at RT
overnight. Diethyl ether was evaporated. The residue was purified
by flash chromatography (silica gel, eluent: hexane) to give a pale
yellow oil (13.24 g).
[0181] Dilithium dimethylsilyl (4-o-biphenyl-2-hexyl indenide)
(4-(3',5'-di-tert-butyl-4'-methoxyphenyl)-2-methyl indenide):
.sup.nBuLi (2.5 M, 14.3 mL, 35.79 mmol) was added to a precooled
solution of the above product (13.20 g, 17.46 mmol) in diethyl
ether (100 mL). The solution was stirred at RT for 3 hours. All
volatiles were removed under vacuum. The residue was washed with
pentane (15 mL.times.2) and dried under vacuum to give the
dilithium compound (12.11 g).
[0182] Dimethylsilyl (4-o-biphenyl-2-hexyl indenyl)
(4-(3',5'-di-tert-butyl-4'-methoxyphenyl)-2-methyl indenyl)
zirconium dichloride: A precooled solution of dilithium
dimethylsilyl (4-o-biphenyl-2-cyclopropyl indenide)
(4-(3',5'-di-tert-butylphenyl)-2-methyl indenide (12.06 g, 15.7
mmol) in toluene (100 mL) was treated with ZrCl.sub.4 (3.79 g, 1.17
mmol). The mixture was stirred at RT overnight. The mixture was
filtered through Celite to get rid of LiCl and evaporated to
dryness. The residue was washed with hexane (50 mL) to get a solid
as a mixture of two isomers. The mixture was recrystallized toluene
(20 mL, 100.degree. C. to 40.degree. C.) to get the corresponding
meso-isomer metallocene (361 mg, ratio of rac/meso=1:22). The
combined filtrate was concentrated and recrystallized (10 mL of
toluene and 5 mL of hexane, refluxed to room temperature) to afford
mixture with rac/meso=15:1. The mixture was further recrystallized
(10 mL of toluene and 6 mL of hexane, refluxed to room temperature)
to obtain the rac-isomer (623 mg, ratio of rac/meso=22:1). .sup.1H
NMR (400 MHz, C.sub.6D.sub.6, 23.degree. C.), rac- form isomer:
.delta. 8.26 (dd, 1H), 7.91 (s, 2H), 7.51 (d, 1H), 7.43 (dd, 1H),
7.36-7.32 (m, 1H), 7.29 (d, 1H)), 7.25 (td, 1H), 7.18-7.09 (m, 5H),
6.95-6.83 (m, 5H), 6.69 (dd, 1H), 3.41 (s, 3H), 2.76-2.66 (m, 1H),
2.48-2.38 (m, 1H), 1.96 (s, 3H), 1.57 (s, 18H), 1.47-1.13 (m, 8H),
0.93-0.87 (m, 6H), 0.65 (s, 3H); meso- form isomer: .sup.1H NMR
(400 MHz, C.sub.6D.sub.6, 23.degree. C.) .delta. 8.22-8.18 (m, 1H),
7.90 (s, 2H), 7.38 (dd, 2H), 7.31-7.28 (m, 2 H), 7.19-7.09 (m, 2H),
7.05-7.71 (m, 3H), 6.96-6.78 (m, 4H), 6.75 (dd, 1H), 6.67 (s, 1H),
6.58 (dd, 1H), 3.39 (s, 3H), 2.81-2.71 (m, 1H), 2.66-2.56 (m, 1H),
2.18 (s, 3H), 1.54 (s, 18 H), 1.40-1.12 (m, 8H), 0.91 (t, 3H), 0.81
(s, 3H), 0.76 (s, 3H).
MCN2 Synthesis:
[0183] 4-([1,1'-Biphenyl]-2-yl)-2-n-Butyl-1H-indene: In glove box,
n-butylmagnesium chloride (18.06 mL, 2.0 M in THF, 36.1 mmol) was
added to a solution of 4-(biphenyl-2-yl)-2-bromo-indene (10.0 g,
28.9 mmol) and PdCl.sub.2(dppf).DCM (0.704 g, 0.867 mmol) in 100 mL
of THF. The reaction was heated up to 40.degree. C. and stirred at
this temperature for 10 hours. The reaction was moved out the glove
box and quenched with 200 mL of water. The mixture was extracted
with toluene (100 mL.times.2). The combined organic phases were
dried over Na.sub.2SO.sub.4 and concentrated under reduced
pressure. The residue was purified by silica gel chromatography
(eluent: hexane) to get the product as a colorless oil (7.82
g).
[0184] Lithium [1-(4-o-biphenyl)-2-butyl-indenide]: A precooled
solution of 4-o-biphenyl-2-butyl-indene (7.80 g, 24.1 mmol) in
diethyl ether (50 mL) was treated with .sup.nBuLi (2.5 M in hexane,
10.1 mL, 25.3 mmol). The reaction was stirred at RT for 3 hours.
Then all volatiles were evaporated. The residue was washed with
hexane (10 mL.times.2) and dried under vacuum to yield an off-white
solid as the product (7.09 g).
[0185] Chlorodimethyl [(4-o-biphenyl)-2-butyl-indenyl] silane: A
precooled solution of lithium [1-(4-o-biphenyl)-2-butyl-indenide]
(3.30 g, 10.0 mmol) in diethyl ether (50 mL) was treated with
Me.sub.2SiCl.sub.2 (6.50 g, 50.0 mmol), and the resulting white
slurry was stirred at RT overnight. All volatiles were evaporated
under reduced pressure. The residue was extracted with hexane (30
mL.times.2), and the combined filtrate was concentrated to dryness
under vacuum to give colorless oil (2.94 g).
[0186] Dimethylsilyl (4-o-biphenyl-2-butyl-indenyl)
trifluoromethanesulfonate: A solution of chlorodimethyl
(4-o-biphenyl-2-butyl-indenyl) silane (2.90 g, 6.97 mmol) in
toluene (30 mL) was treated with silver trifluoromethanesulfonate
(1.96 g, 7.67 mmol) while stirring. The white slurry was stirred at
RT for 5 hours. Toluene was evaporated under vacuum and the residue
was extracted with hexane (30 mL.times.2). The filtrate was
concentrated under vacuum to give colorless oil as the product
(3.60 g).
[0187] Bis(4-o-biphenyl-2-butyl-indenyl) dimethylsilane: A
precooled solution of dimethylsilyl (4-o-biphenyl-2-butyl-indenyl)
trifluoromethanesulfonate (3.50 g, 6.60 mmol) in diethyl ether (30
mL) was treated with lithium [1-(4-o-biphenyl)-2-butyl-indenidel
(2.18 g, 6.60 mmol). The solution was stirred for 3 hours at room
temperature. Diethyl ether was evaporated. The residue was
extracted with solvents (mixed with 30 mL of toluene and 30 mL of
hexane). The combined filtrate was concentrated and further dried
over vacuum to get an off-white solid as the product (3.24 g).
[0188] Dilithium dimethylsilyl bis(4-o-biphenyl-2-butyl-indenide):
.sup.nBuLi (2.5 M, 3.7 mL, 9.26 mmol) was added to a precooled
solution of bis(4-o-biphenyl-2-butyl-indenyl) dimethylsilane (3.18
g, 4.52 mmol) in diethyl ether (30 mL). The solution was stirred at
RT for 3 hours. All volatiles were removed under vacuum. The
residue was washed with hexane (10 mL.times.2) and dried under
vacuum to give pale yellow foam (2.45 g).
[0189] Dimethylsilyl bis(4-o-biphenyl-2-butyl-indenyl) zirconium
dichloride: A precooled solution of dilithium dimethylsilyl
bis(4-o-biphenyl-2-butyl-indenide) (2.37 g, 3.31 mmol) in toluene
(30 mL) was treated with ZrCl.sub.4 (0.76 g, 3.31 mmol). The
mixture was stirred at RT overnight. The mixture was then
evaporated to dryness. The residue was extracted with hot
cyclohexane (50 mL). The combined filtrate was concentrated under
reduced pressure and washed with hexane (20 mL) to get an orange
solid as a mixture of two isomers. The mixture was recrystallized
(2 mL of toluene and 18 mL hexane, refluxed to room temperature) to
afford mixture (520 mg, wet, ratio of rac/meso=10:1). Then the
mixture was further recrystallized (1.5 mL of toluene and 13.5 mL
hexane, refluxed to room temperature) to afford the rac-isomer (100
mg, ratio of rac/meso=68:1). .sup.1H NMR (400 MHz, C.sub.6D.sub.6,
23.degree. C.), rac- form isomer: .delta. 8.26-8.23 (m, 2H), 7.38
(d, 2H), 7.35-7.30 (m, 2H), 7.22-7.12 (m, 4H), 7.10-7.05 (m, 6H),
6.90-6.78 (m, 8H), 6.70 (dd, 2H), 2.66-2.55 (m, 2H), 2.41-2.30 (m,
2H), 1.29-1.19 (m, 4H), 1.13-1.02 (m, 4H), 0.81 (t, 6H), 0.75 (s,
6H).
MCN3 Synthesis:
[0190] MCN3 was synthesized as provided in Organometallics, 2011,
30 (21), pages 5744-5752.
MCN4 Synthesis:
[0191] Lithium {1-[(4-o-biphenyl-2-.sup.nhexyl) indenide]}:
.sup.nBuLi (2.5 M, 8.2 mL, 20.5 mmol) was added to a stirring
precooled solution of
4-([1,1'-Biphenyl]-2-yl)-2-.sup.nHex-1H-indene (6.55 g, 18.58 mmol)
in diethyl ether (100 mL). The solution was stirred at RT for 19
hours. All volatiles were evaporated. The residue was dried under
vacuum to give a crude product containing 0.08 equiv. of Et.sub.2O
(6.07 g). The product was used without further purification.
[0192] Chlorodimethyl[4-o-biphenyl-2-.sup.nhexyl-indenyl]silane:
Me.sub.2SiCl.sub.2 (10 g, 77.48 mmol) was added to a precooled
solution of above lithium salts (1.97 g, 5.40 mmol) in diethyl
ether (60 mL). Additional diethyl ether (10 mL) was added. The
white slurry was stirred at RT for 17 hours. All volatiles were
removed in vacuo. The residue was extracted with hexane (50 mL
once, 10 mL once) and the filtrate was concentrated under vacuum to
give the product (2.19 g). The product was used without further
purification.
[0193] Dimethylsilyl[4-o-biphenyl-2-.sup.nhexyl-indenyl]
trifluoromethanesulfonate: Silver trifluoromethanesulfonate (1.31
g, 5.098 mmol) was added to a stirring solution of above product
(2.16 g, 4.853 mmol) in toluene (25 mL). Additional toluene (10 mL)
was added. The slurry was stirred at RT for 1 hour. Toluene was
removed under vacuum and the residue was extracted with hexane (40
mL once, 10 mL once). The hexane filtrate was concentrated under
vacuum to give the product (2.55 g). The product was used without
further purification.
[0194] Bis(4-o-Biphenyl-2-.sup.nhexyl-indenyl) dimethylsilane:
Lithium {1-[1-[(4-o-biphenyl-2-.sup.nhexyl) indenide[}
(Et.sub.2O).sub.0.08 (1.62 g, 4.446 mmol) was added to a precooled
solution of dimethylsilyl[4-o-biphenyl-2-.sup.nhexyl-indenyl]
trifluoromethanesulfonate (2.48 g, 4.439 mmol) in diethyl ether (40
mL). Additional diethyl ether (10 mL) was added. The reaction was
stirred at RT for 19 hours. All volatiles were evaporated. The
residue was extracted with hexane (50 mL once, 10 mL once) and the
filtrate was concentrated under vacuum to give the crude product
(3.28 g). The product was used without further purification.
[0195] Dilithium dimethylsilyl
bis(4-o-biphenyl-2-.sup.nhexyl-indenide): .sup.nBuLi (2.5 M, 3.5
mL, 8.75 mmol) was added to a precooled solution of the above crude
product (3.22 g) in diethyl ether (30 mL) and hexane (15 mL). The
solution was stirred at RT for 24 hours. All volatiles were removed
under vacuum. The residue was washed with hexane (20 mL twice) and
dried under vacuum to give the crude product containing 0.54 equiv.
of Et.sub.2O (3.29 g).
[0196] Dimethylsilyl bis(4-o-Biphenyl-2-.sup.nhexyl-indenyl)
zirconium dichloride: ZrCl.sub.4 (0.96 g, 4.119 mmol) was added to
a precooled solution of the above crude product (3.27 g) in toluene
(40 mL). Additional toluene (10 mL) was added. The mixture was
stirred at RT for 18 hours. All volatiles were removed under
vacuum. The residue was extracted with hexane (60 mL once, 10 mL
once). The hexane insolubles were then extracted into toluene (40
mL once, 10 mL once). Toluene filtrates were concentrated to
dryness under vacuum to give crude product as a rac/meso mixture in
1/1.2 ratio (1.15 g). Toluene (4 mL) and hexane (32 mL) were added.
The slurry was heated to reflux and then was cooled back to room
temperature. The mixture was stirred at RT for 3 days. The
precipitates were separated, washed with hexane (5 mL twice), and
dried in vacuo to give a solid with rac/meso ratio of 1/1.6 (0.99
g). Further multiple fractional crystallizations from diethyl ether
afforded a crude product (0.28 g) with rac/meso ratio of about 50/1
plus some insoluble impurities. To this crude product was added
CH.sub.2Cl.sub.2 (18 mL). The mixture was filtered and the
insolubles were washed with additional CH.sub.2Cl.sub.2 (18 mL
once, 5 mL once). The filtrate and washings were combined and
evaporated to dryness. The solid obtained was washed with diethyl
ether (5 mL) and dried in vacuo to afford the product (0.15 g,
rac/meso=40/1). .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2, 23.degree.
C.): rac: .delta. 7.64 (m, 2H), 7.49 (m, 2H), 7.40-7.46 (m, 6H),
7.11 (m, 2H), 7.04-7.08 (m, 10H), 6.91 (m, 2H), 6.32 (s, 2H), 2.54
(m, 2H), 2.10 (m, 2H), 1.32-1.08 (m, 22H), 0.88 (t, 6H).
[0197] MCN5 Synthesis: MCN5 was synthesized as described in US
Patent Publication 2015/0025208.
[0198] MCN6 and MCN7 Synthesis: MCN6 and MCN7 were synthesized as
described in U.S. Pat. No. 9,279,024.
MCN8 Synthesis:
[0199] Chlorodimethyl (4-o-biphenyl-2-butyl-inden-1-yl) silane: A
precooled solution of lithium [1-(4-o-biphenyl)-2-butyl-indenide]
(3.30 g, 10.0 mmol) in diethyl ether (50 mL) was treated with
Me.sub.2SiCl.sub.2 (6.45 g, 50.0 mmol), and the resulting white
slurry was stirred over night at room temperature. All volatiles
were evaporated. The residue was extracted with hexane
(20mL.times.2), and the combined filtrate was concentrated under
reduced pressure to get colorless oil (3.91 g).
[0200] Dimethylsilyl (4-o-biphenyl-2-butyl-inden-1-yl)
trifluoromethanesulfonate: A precooled solution of chlorodimethyl
(4-o-biphenyl-2-butyl-inden-1-yl) silane (3.90 g, 9.4 mmol) in
toluene (30 mL) was treated with silver trifluoromethanesulfonate
(2.64 g, 10.3 mmol) while stirring. The white slurry was stirred
for 3 hours at room temperature. Toluene was removed under reduced
pressure, and the residue was extracted with hexane (20
mL.times.2). The collected filtrate was concentrated under reduced
pressure to colorless oil as the product (4.88 g).
[0201]
4,4,5,5-Tetramethyl-2-(6-methyl-1,2,3,7-tetrahydro-s-indacen-4-yl)--
1,3,2-dioxaborolane: A mixture of
8-bromo-6-methyl-1,2,3,5-tetrahydro-s-indacene (24.8 g, 100 mmol),
bis(pinacolato)diboron (25.4 g, 100 mmol), powdered anhydrous
potassium acetate (19.6 g, 200 mmol),
bis(triphenylphosphine)palladium(II) dichloride (3.50 g, 5.0 mmol),
and DMF (100 mL) was refluxed under N.sub.2 for 10 hours. The
mixture was poured into 800 mL of water and extracted with toluene
(2.times.100 mL). The combined organic phases were dried over
MgSO.sub.4 and concentrated in vacuo. The residue was purified by
silica gel chromatography (eluent: hexane) to yield product as a
white solid (24.30 g).
[0202]
8-(3',5'-Di-tert-butyl-4'-methoxyphenyl)-6-methyl-1,2,3,5-tetrahydr-
o-s-indacene: A mixture of
5-bromo-1,3-di-tert-butyl-2-methoxybenzene (7.07 g, 23.65 mmol),
4,4,5,5-Tetramethyl-2-(6-methyl-1,2,3,7-tetrahydro-s-indacen-4-yl)-1,3,2--
dioxaborolane (7.00 g, 23.65 mmol), potassium carbonate (4.90 g,
35.5 mmol), tetrabutylammonium bromide (1.57 g, 4.73 mmol),
bis(triphenylphosphine)palladium(II) dichloride (0.50 g, 0.71
mmol), water (100 mL) and ethanol (10 mL) was refluxed for 5 hours.
The reaction was cooled down and extracted with hexane (2.times.200
mL). The combined organic layers were washed with water (100 mL),
dried over MgSO.sub.4, and concentrated under reduced pressure. The
resulting residue was purified by silica gel column (eluent:
hexane) to obtain product as a white solid (8.39 g).
[0203] Lithium
{4-(3',5'-di-tert-butyl-4'-methoxyphenyl)-2-methyl-1,5,6,7-tetrahydro-s-i-
ndacenide}: A precooled solution of
8-(3',5'-di-tert-butyl-4'-methoxyphenyl)-6-methyl-1,2,3,5-tetrahydro-s-in-
dacene (3.88 g, 10.0 mmol) in diethyl ether (20 mL) was treated
with .sup.nBuLi (2.5 M in hexane, 4.2 mL, 10.5 mmol). The reaction
was stirred over night at room temperature. Then all volatiles were
evaporated. The residue was washed with hexane (20 mL.times.2) and
dried under vacuum to yield an orange solid (3.60 g).
[0204] (4-o-Biphenyl-2-butyl-indenyl)
(4-(3',5'-di-tert-butyl-4'-methoxyphenyl)-2-methyl-1,5,6,7-tetrahydro-s-i-
ndacenyl) dimethylsilane: A precooled solution of dimethylsilyl
(4-o-biphenyl-2-butyl-inden-1-yl) trifluoromethanesulfonate (4.80
g, 9.06 mmol) in diethyl ether (30 mL) was treated with a solid of
lithium
1-[4-(3',5'-di-tert-butyl-4'-methoxyphenyl)-2-methyl-1,5,6,7-tetrahydro-s-
-indacenide] (3.57 g, 9.06 mmol). The solution was stirred
overnight at room temperature. Diethyl ether was evaporated. The
residue was extracted with hexane (30 mL.times.2). The combined
filtrate was concentrated to dryness and dried over vacuum to get
colorless foam (6.70 g).
[0205] Dilithium dimethylsilyl (4-o-biphenyl-2-butyl indenide)
(4-(3',5'-di-tert-butyl-4'-methoxyphenyl)-2-methyl-1,5,6,7-tetrahydro-s-i-
ndacenide): .sup.nBuLi (2.5 M, 7.1 mL, 17.83 mmol) was added to a
precooled solution of
(4-o-biphenyl-2-butyl-indenyl)(4-(3',5'-di-tert-butyl-4'-methoxyphenyl)-2-
-methyl-1,5,6,7-tetrahydro-s-indacenyl) dimethylsilane (6.68 g,
8.70 mmol) in diethyl ether (50 mL). The mixture was stirred for 3
hours at room temperature. All volatiles were removed under reduced
pressure. The residue was washed with cool hexane (30 mL) and dried
under vacuum to yield an orange solid (6.247 g).
[0206] Dimethylsilyl (4-o-biphenyl-2-butyl indenyl)
(4-(3',5'-di-tert-butyl-4'-methoxyphenyl)-2-methyl-1,5,6,7-tetrahydro-s-i-
ndacenyl) zirconium dichloride: A precooled solution of dilithium
dimethylsilyl (4-o-biphenyl-2-butyl indenide)
(4-(3',5'-di-tert-butyl-4'-methoxyphenyl)-2-methyl-1,5,6,7-tetrahydro-s-i-
ndacenide) (6.20 g, 7.95 mmol) in toluene (50 mL) was treated with
a powder of ZrCl.sub.4 (1.83 g, 7.95 mmol). The mixture was stirred
for 5 hours at room temperature. Then the mixture was concentrated
under reduced pressure, and the residue was extracted with solvents
(mixed with 25 mL of toluene and 20 mL of hexane). The combined
filtrate was concentrated. The resulting residue was recrystallized
(10 mL of toluene and 50 mL of hexane, refluxed to room
temperature). Then the collected solid was further recrystallized
(30 mL of toluene, refluxed to room temperature) to get the
meso-isomer (853 mg, ratio of rac/meso<1:100). The filtrate from
the first recrystallization was concentrated and the residue was
recrystallized (10 mL of toluene and 50 mL of hexane, refluxed to
room temperature) to afford rac-isomer (351 mg, ratio of
rac/meso=39:1). .sup.1H NMR (400 MHz, C.sub.6D.sub.6, 23.degree.
C.), meso-form isomer: .delta. 8.23-8.17 (m, 1H), 7.83 (bs, 2H),
7.52 (d, 1H), 7.38 (s, 1H), 7.32-7.28 (m, 1H), 7.22-7.03 (m, 4H),
6.97 (dd, 1H), 6.88-6.77 (m, 4H), 6.63-6.57 (m, 2H), 3.45 (s, 3H),
3.08-2.55 (m, 6H), 2.16 (s, 3H), 1.85-1.65 (m, 2H), 1.55 (s, 18H),
1.45-1.16 (m, 2H), 1.16-1.08 (m, 2H), 0.91 (s, 3H), 0.85 (t, 3H),
0.76 (s, 3H); rac-form isomer: .delta. 8.28 (dd, 1H), 7.84 (bs,
2H), 7.46 (s, 1H), 7.37-7.23 (m, 3H), 7.19-7.08 (m, 4H), 6.97 (s,
1H), 6.94-6.83 (m, 4H), 6.68 (dd,1H), 3.47 (s, 3H), 3.12-3.02 (m,
1H), 2.98-2.72 (m, 4H), 2.50-2.40 (m, 1H), 1.95 (s, 3H), 1.84-1.72
(m, 2H), 1.59 (s, 18H), 1.38-1.10 (m, 4H), 0.94 (s, 3H), 0.87 (t,
3H), 0.69 (s, 3H).
[0207] Supportation: Silica was obtained from the Asahi Glass Co.,
Ltd. or AGC Chemicals Americas, Inc. (D170-120A), PQ Corporation
(PD 14024), and Davison Chemical Division of W.R. Grace and Company
(Davison 948).
[0208] Raw silica was calcined at the desired temperature (Tc,
Table 2 below) using a tube furnace. Silica was poured into quartz
tube which had N.sub.2 flowing through the bottom to remove water
vapor and also keep the silica in an inert atmosphere. Temperature
and time requirements were fed into the tube furnace controller.
Silica was calcined for about 8 hours to allow proper removal of
water/moisture. Carbolite Tube Furnace Model VST 12/600 was used as
the heating device, and the temperature was controlled by a
Eurotherm 3216P1 temperature controller.
[0209] The quartz tube was filled with desired amount of silica
(Ms, Table 2) and the N.sub.2 valve was turned on. The nitrogen
pressure was adjusted so that the silica was fluidized completely.
The quartz tube was then placed inside the heating zone of the
furnace. The temperature controller was used to control the heating
and cooling manually. Its program contains up to 8 ramps and 8
dwelling segments. Silica was heated slowly to desired temp and
then hold temp for at least 8 hours to allow complete calcination.
After the dehydration was complete, the quartz tube was cooled down
to RT. Calcined silica was collected in a silica catcher and
brought inside the dry box where it was collected into a glass
container. Diffuse Reflectance Infrared Fourier Transform
Spectroscopy (DRIFTS) was done on calcined silica to quality
control the calcination. Additional properties of the calcined
silica are shown in Table 2 below.
TABLE-US-00002 TABLE 2 Silica Data and Calcination Conditions Tc Ms
Time PS SA PV PD Silica# (.degree. C.) (g) (hr) (.mu.m) (m.sup.2/g)
(mL/g) (.ANG.) 1 PQ PD-14024 200 100 8 85 611 1.40 92 2 AGC
D70-120A 600 100 8 70 450 1.64 146
[0210] Supported MAO (sMAO) Preparation: MAO was obtained as a 30
wt % MAO in toluene solution from Albemarle (13.5 wt % Al or 5.0
mmol/g). In a 125 mL Celstir reactor, silica (amount in Table 3)
was weighted and slurried into 6.times. toluene (e.g., 1 g silica,
6 g toluene). Silica slurry was stirred at 500 rpm to get a
homogeneous mixture. MAO (30% toluene solution, amount in Table 3)
was added very slowly into the silica slurry to maintain the
temperature <40.degree. C. After the completion of addition, the
mixture was stirred for 30 minutes at RT and 350 rpm, and then
heated at 100.degree. C. for 3 hours. The slurry was cooled to RT
and filtered through a medium frit. The filtrate mixed with
THF-d.sub.8 was analyzed with .sup.1H NMR spectroscopy and no
significant MAO was detected. The wet solid was washed once with
10.times. silica mass of toluene to remove possible unreacted MAO,
then washed twice with 10.times. silica mass of hexane [e.g., if
silica is 2 g, the solvent for each wash is 10.times.2=20 g], and
then dried under vacuum for 3 hrs, yielding dry sMAO (yield in
Table 3).
TABLE-US-00003 TABLE 3 Supported MAO Preparation Conditions Amount
Silica Mass of 30% MAO Load.sup.a Yield sMAO# Silica (g) MAO (g)
(mmol/g SiO.sub.2) (g) 1 PD14024 10.0 26.43 13 17.85 2 D70-120A
10.0 24.64 12 18.06.sup.b .sup.aMAO charge is based on the Al wt %
of the Albemarle commercial MAO toluene solution provided by the
vendor. Al wt % changes from batch to batch, ranging from 13.2-13.8
wt %; typical 13.5 wt %. .sup.bWet.
[0211] For comparison to similar catalysts supported on Grace
Davison Silica 948, please see FIG. 3 in concurrently filed PCT
Application ______, (Atty. Docket 2016EM112) entitled "Metallocene
Catalyst Compositions and Polymerization Process Therewith"), which
is fully incorporated herein by reference.
[0212] Catalyst Preparation (Catalysts A-G): In a 25 mL Celstir
reactor or a 20 mL vial, sMAO (amount in Table 4) and 5.times.
toluene (e.g., 1 g sMAO, 5 g toluene) were added. The slurry was
stirred at 350 rpm (Celstir) or place on a shaker (vial) to get a
homogeneous mixture. TIBAL (neat) at an amount of 0.34 mmol/g sMAO
was added slowly into the sMAO slurry and stirred for 15 minutes.
Then, the metallocene was added and the mixture was stirred for 1
to 2 hours at RT. The slurry was filtered through a medium frit.
The wet solid was washed twice with 10.times. sMAO (amount in Table
4) of toluene to remove excess soluble catalyst, then washed once
with 10.times. sMAO of hexane, and then dried under vacuum for 3
hours, yielding free flow solid supported catalysts (yield in Table
4).
TABLE-US-00004 TABLE 4 Finished Catalyst Preparation Conditions and
Polymerization Results sMAO Zr* Yield Catalyst MCN/Silica (g) (%)
(g) Catalyst A MCN1/PD14024 1.0 0.12 0.98 Catalyst B MCN1/D70-120A
15.0 0.12 14.2 Catalyst C MCN2/PD14024 1.0 0.16 0.99 Catalyst D
MCN3/PD14024 1.0 0.16 0.97 Catalyst E MCN4/PD14024 1.0 0.12 1.0
Catalyst F MCN5/PD14024 1.0 0.16 1.0 Catalyst G MCN8/PD14024 1.0
0.16 1.0 *Based on charge.
[0213] Catalyst Preparation (Catalysts H and I): Catalysts H and I
were prepared as described in U.S. Pat. No. 9,279,024.
Propylene Polymerization with Supported Catalysts:
[0214] Polymerization was performed in a 2-liter batch ZipperClave
stirred reactor equipped with a water jacket for temperature
control. A catalyst slurry was prepared by mixing solid catalyst
with degased mineral oil as a 5 wt % slurry.
[0215] Prepolymerization: For the examples in Tables 5a, 5b, and 6,
1.0 g of slurry catalyst was charged to a catalyst tube in the dry
box for the 0 psi H.sub.2 runs, or 0.5 g slurry catalyst for the 20
psi H.sub.2 runs and the staged H.sub.2 addition run, followed by 1
ml hexane (N.sub.2 spared and sieves purified). The only exception
is that for the example of Tables 5a and 5b, Run 2, 1 g slurry
catalyst was used for both the 0 psi H.sub.2 run and the 20 psi
H.sub.2 run. Then, 1.75 ml TIBAL was charged to a 3 mL syringe (7.6
mL neat tri-isobutylaluminum+hexane to 100 mL, 7.6 vol %). The
catalyst tube and the 3 ml syringe containing TIBAL were removed
from the dry box and attached to the reactor while the reactor was
being purged with nitrogen. The TIBAL solution in the syringe was
injected into the reactor via a scavenger port capped with a rubber
septum. The scavenger port valve was then switched off.
[0216] Propylene (1000 ml) was then introduced to the reactor
through a purified propylene line. The agitator was brought to 500
rpm. The mixture was allowed to mix for 5 minutes at RT. The
catalyst slurry in the catalyst tube was then flushed into the
reactor with 250 ml propylene. The polymerization reaction was
allowed to run for 5 minutes at RT.
[0217] For the polymerizations in Table 5a under the 0 psi H.sub.2
conditions, the temperature was increased to 70.degree. C. and held
for 40 minutes. For the polymerizations in Table 5b under the 20
psi H.sub.2 conditions, after increasing the temperature to
70.degree. C., a 150 mL bomb with 20 psi H.sub.2 was opened to the
reactor and the reaction was allowed to run for 40 minutes at
70.degree. C. after the H.sub.2 charge. For the staged H.sub.2
addition polymerization in Table 6, under the 0 psi H.sub.2
condition, the temperature was increased to 70.degree. C. and held
for 40 minutes. After this, a 150 mL bomb with 55 psi H.sub.2 was
opened to the reactor and the reaction was allowed to run for
another 10 minutes.
[0218] After the process described above, the reactor was quickly
vented to stop the polymerization using the reactor vent block
valve. The bottom of the reactor was dropped and a polymer sample
was collected. Reaction conditions, catalyst activities, and
polymer MFR data are summarized in Tables 5a, 5b, and 6 below.
TABLE-US-00005 TABLE 5a Propylene Polymerizations at 70.degree. C.,
No H.sub.2 for 40 Min Activity Yield (g polymer/ Tm Mw Run Catalyst
Conditions (g) g cat hr) MFR (.degree. C.) (kg/mol) Mw/Mn 1
Catalyst D No H.sub.2 for 39.75 1200 0.41 154.4 (Comparative) 40
min 2 Catalyst E No H.sub.2 for 31.75 950 0.015 151.7 (Comparative)
40 min 3 Catalyst F No H.sub.2 for 92.44 2800 8.9 154.3 289 2.0
(Comparative) 40 min 4 Catalyst A No H.sub.2 for 127.42 3800 0.11
152.3 636 2.5 40 min 5 Catalyst C No H.sub.2 for 133.62 4000 0.037
1475 2.0 40 min 6 Catalyst B No H.sub.2 for 104.72 3100 0.33 152.3
730 3.2 40 min 7 Catalyst G No H.sub.2 for 143.05 4300 0.16 152.6
1094 2.3 40 min
TABLE-US-00006 TABLE 5b Propylene Polymerizations at 70.degree. C.,
20 psi H.sub.2 for 40 Min Activity Yield (g polymer/ Tm Mw Run
Catalyst Conditions (g) g cat hr) MFR (.degree. C.) (kg/mol) Mw/Mn
1 Catalyst D 20 psi H.sub.2 191.85 12000 267 155.9 115 2.9
(Comparative) for 40 min 2 Catalyst E 20 psi H.sub.2 90.96 2700 47
153.2 209 5.0 (Comparative) for 40 min 3 Catalyst F 20 psi H.sub.2
192.53 12000 810 155.8 105 2.7 (Comparative) for 40 min 4 Catalyst
A 20 psi H.sub.2 177.76 11000 150 151.4 128 2.6 for 40 min 5
Catalyst C 20 psi H.sub.2 191.1 11000 30 249 2.5 for 40 min 6
Catalyst B 20 psi H.sub.2 313.43 19000 840 153.7 150 2.4 for 40 min
7 Catalyst G 20 psi H.sub.2 250.34 15000 199 154.1 113 2.5 for 40
min
[0219] As seen from Run 1 in Tables 5a and 5b, comparative Catalyst
D (MCN3 supported on PD14024) produces a low Mw iPP (high MFR)
polymer at high catalyst activities in the presence of H.sub.2.
However, in the absence of H.sub.2 it has low activity and gives
iPP with moderately high Mw. Run 2 in Tables 5a and 5b shows that
comparative Catalyst E (MCN4 on the same silica support) gives very
high Mw iPP (as suggested by the MFR of 0.015), but with very low
activities. Run 3 shows that comparative Catalyst F (MCNS on the
same silica) has quite high activity in the absence of H.sub.2 and
the iPP obtained has relatively low Mw. Under the same supportation
conditions, Runs 4 and 5 show that inventive Catalyst A (MCN1
supported on PD14024) and inventive Catalyst C (MCN2 supported on
PD14024) show a combination of high Mw capability (low MFR) and
high activity in the absence of H.sub.2. Run 6 shows that inventive
Catalyst B (MCN1 supported on D70-120A) also has excellent catalyst
activity and high Mw capability. Run 7 shows that inventive
Catalyst G (MCN8 supported on PD14024) also has excellent catalyst
activity and high Mw capability (low MFR).
[0220] To further illustrate the importance of these findings,
Catalyst A was used for a staged H.sub.2 addition polymerization
run to produce bimodal iPP. As seen from Table 6, Run 8 below, this
catalyst demonstrated high overall activities and capabilities for
very broad MWD. Runs 9 and 10 summarized in Table 6 below are
comparative and from U.S. Pat. No. 9,279,024 (Table 1, Examples 16
and 24 respectively), and use catalyst systems similar or identical
to comparative Catalysts H and I described herein. Comparing Run 8
with Runs 9 and 10 shows that the bimodal iPP obtained from
inventive Catalyst A has superior stiffness properties (1% Sec Flex
Modulus of 2020 MPa) over the bimodal iPPs made with Catalysts H
and I at similar MFRs.
TABLE-US-00007 TABLE 6 Bimodal iPP Polymerization at 70.degree. C.
with Staged H.sub.2 Addition Activity (g polymer/ Mw 1% Sec Flex
Run Catalyst Conditions g cat hr) MFR (k) MWD (MPa) 8 Catalyst A No
H.sub.2 for 40 min, 5500 79 284 18.4 2020 55 psi H.sub.2 for 10 min
9 Catalyst H U.S. Pat. No. 9,279,024; 2040 53 194 7.6 1740
(Comparative) Table 1 Example 16 10 Catalyst I U.S. Pat. No.
9,279,024; 1820 46 332 14.8 1686 (Comparative) Table 1 Example
24
[0221] FIG. 4 is a graph of the polymer MWD from DRI Analysis for
the bimodal polypropylene produced according to the example in
Table 6, Run 8.
[0222] All documents described herein are incorporated by reference
herein for purposes of all jurisdictions where such practice is
allowed, including any priority documents, related application
and/or testing procedures to the extent they are not inconsistent
with this text. As is apparent from the foregoing general
description and the specific embodiments, while forms of the
invention have been illustrated and described, various
modifications can be made without departing from the spirit and
scope of the invention. Accordingly, it is not intended that the
invention be limited thereby. Likewise, the term "comprising" is
considered synonymous with the term "including." Likewise whenever
a composition, an element or a group of elements is preceded with
the transitional phrase "comprising", it is understood that we also
contemplate the same composition or group of elements with
transitional phrases "consisting essentially of", "consisting of",
"selected from the group of consisting of", or "is" preceding the
recitation of the composition, element, or elements and vice
versa.
* * * * *